Fibers with chemical markers used for coding

ABSTRACT

Disclosed are fibers which contain identification fibers. The identification fibers can comprise one or more chemical markers, or taggants, which may vary among the fibers or be incorporated throughout all of the fibers. The disclosure also relates to the method for making and characterizing the fibers. Characterization of the fibers can include identifying chemical markers and correlating the chemical markers and a taggant chemical marker amounts of at least one of the chemical markers to manufacturer-specific taggants to determine supply chain information. The supply chain information can be used to track the fibers from manufacturing through intermediaries, conversion to final product, and/or the consumer.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. 119(e) to U.S.Provisional Application No. 62/018,192, filed Jun. 27, 2014 and U.S.Provisional Application No. 62/105,022 filed Jan. 19, 2015, both ofwhich are incorporated herein by reference in their entirety.

TECHNICAL FIELD

The disclosed embodiments relate to fibers comprising identificationfibers. The identification fibers can contain a plurality of chemicalmarkers, or taggants, which may vary among the fibers or be incorporatedthroughout all of the fibers. The chemical markers can be representativeof specific supply chain information. The supply chain information canbe used to track the fibers from manufacturing through intermediaries,conversion to final product, and/or the consumer. The disclosedembodiments also relates to the method for making and characterizing thefibers. Characterization of the fibers can include identifying chemicalmarkers and correlating the chemical markers to manufacturer-specifictaggants to determine supply chain information.

BACKGROUND

Many industries have a need to mark, tag, or identify products thatallows for the tracking and tracing of products through the supplychain. One of the primary purposes for such track and trace systems isthe combating of illicit trade such as counterfeiting and black marketsales.

Anti-counterfeiting measures (AGMs) can be regarded as three differenttypes: Type I (Overt), Type II (Covert) and Type III (Forensic). Type IAGMs are features incorporated into an article that are readilyidentified and observable to the naked eye. Examples include watermarks,color shifting inks, colored fibers, bands, or strips incorporated intothe article, and holograms. Type II AGMs are features that areincorporated into the article that require some form of instrument toidentify the feature in the field. The instruments required aregenerally those that are readily available and transportable. Someexamples include the incorporation of very small text (requiring the useof a magnifying glass), UV responsive inks or threads (requiringillumination with a UV light), and barcodes or RFID tags (requiring aspecialized reader). Type III AGMs are hidden attributes that requirespecialized laboratory equipment to identify. Some Type III examplesinclude nano-text, micro-taggants, DNA inks, and chemical additives.

As stated above, there are many widely-used packaging and labellingtaggants and anti-counterfeiting measures (AGMs) in many industries, butthese more overt solutions are often susceptible to countermeasures suchas destruction, modification, duplication, repackaging, or relabeling.Altering the chemical properties of the raw materials of a product canprovide a more covert solution that is much more difficult to evade.These taggants may be used to track the fibers through the supply chain.The taggants may change the chemical properties of the fibers, yarn,fiber bands, and/or derivative articles in a manner that is difficult tocopy or alter but is detectable using standard chemical analysistechniques.

There is a need to manufacture, test, and track fibers in yarn and/orfiber bands and their derivative articles across a wide spectrum ofindustries. The ability to identify the source of a yarn, fiber band,and/or an article comprising the yarn or fiber band can be achieved byembedding some form of a code in the fiber(s) during the manufacturingprocess that can then be later identified, retrieved, and used toidentify the yarn, fiber band and/or the article. Identification tagscan be incorporated into the yarn or fiber band that can denote, forexample, manufacturer, manufacture site, customer, and ship-to locationamong other supply chain information that might be useful for the trackand trace of the fiber band and/or article.

The disclosed exemplary embodiments can be used, for example, to combatthe continuing and growing illicit-trade problem of tobacco products,particularly cigarettes. It has been estimated that 10-12% of allcigarette sales are illicit, either counterfeit copies or sales thatavoid paying excise taxes on the cigarettes (Tobacco International,“Tackling Illicit Trade, Pt. I,” December 2013). To combat this illicittrading requires a global effort consisting of manufacturers,distributors, regulators and customs/law enforcement as well as theretailer who sell the cigarettes to the consumers. There is a need to beable to track and ultimately trace components used in the constructionof a cigarette. For example, the ability to track part of the supplychain path of acetate tow contained in the filter of a black marketcigarette may give helpful information on the source of these illicitcigarettes.

There is a need for a traceable acetate tow that is readilymanufactured, does not impact the performance of a cigarette filter, andis detectable, not only in an acetate tow band, but also in a single ora set of cigarettes/cigarette filters. There is a need for traceableacetate tow that does not impact the pressure drop and yield of acigarette filter. There is a need for traceable acetate tow thatmaintains its traceability when bloomed, plasticized, and formed into afilter.

BRIEF SUMMARY

In a first embodiment, fibers comprise identification fibers, whereinthe identification fibers comprise 1 to 100 chemical markers. The amountof each of the chemical markers, based on a weight of the fibers, isdefined as a chemical marker amount. The chemical markers and thechemical marker amounts are representative of at least one supply chaincomponent of the fibers.

In a second embodiment, an acetate tow band comprises fibers comprisingstandard fibers and identification fibers. The standard fibers comprisecellulose acetate. The identification fibers comprise 1 to 20 chemicalmarkers. The amount of each of the chemical markers, based on a weightof the fibers, is defined as a chemical marker amount. The chemicalmarkers and the chemical marker amounts are representative of at leastone supply chain component of the acetate tow band.

In a third embodiment, a method for making an acetate tow band comprisesfibers comprising standard fibers and identification fibers. Thestandard fibers comprise cellulose acetate. The method comprises (a)obtaining the identification fibers, wherein the identification fiberscomprise 1 to 20 chemical markers; (b) producing the standard fibers ona first fiber production process; and (c) combining the standard fiberswith the identification fibers into the acetate tow band. The amount ofeach of the chemical markers, based on a weight of the fibers, isdefined as a chemical marker amount. The chemical markers and thechemical marker amounts are representative of at least one supply chaincomponent of the acetate tow band.

In a fourth embodiment, a method for characterizing a fiber samplecomprising fibers. The fibers comprise standard fibers andidentification fibers. The identification fibers comprise 1 to 100chemical markers. The amount of each of the chemical markers, based on aweight of the fibers, is defined as a chemical marker amount. Thechemical markers and the chemical marker amounts are representative ofat least one supply chain component of the acetate tow band. The methodcomprises: (a) dissolving the fiber sample in a solvent to produce asample solution and/or insolubles; (b) analyzing the sample solutionand/or the insoluble to identify the chemical markers and each of thechemical marker amounts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B illustrates a non-limiting example of communication andshipping channels consistent with disclosed embodiments.

FIG. 2 illustrates a non-limiting example of a computing system used byone or more entities consistent with disclosed embodiments.

FIG. 3 illustrates a non-limiting example of a process for embeddingsupply chain information into fibers.

FIG. 4 illustrates a non-limiting example of a process for generatingcorrelation data mapping chemical markers to supply chain information.

FIG. 5 illustrates a non-limiting example of a process for generatingcorrelation data mapping chemical markers to supply chain information.

FIG. 6 illustrates a non-limiting example of a process for producingidentification fibers.

FIG. 7 illustrates a non-limiting example of a process for identifyingsupply chain information from a sample.

FIG. 8 illustrates a non-limiting example of a process for identifyingchemical markers from identification fibers.

FIG. 9 illustrates a non-limiting example of a process for assigning, tosupply chain components, taggant information that uniquely represent thesupply chain components.

DETAILED DESCRIPTION

The disclosed embodiments provide fibers comprising identificationfibers, wherein the identification fibers comprise 1 to 100 chemicalmarkers. The amount of each of the chemical markers, based on a weightof the fibers, is defined as a chemical marker amount. The chemicalmarkers and the chemical marker amounts are representative of at leastone supply chain component of the fibers.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the specification and claims are to be understoodas being modified in all instances by the term “about.”

It is to be understood that the mention of one or more process stepsdoes not preclude the presence of additional process steps before orafter the combined recited steps or intervening process steps betweenthose steps expressly identified. Moreover, the lettering of processsteps or ingredients is a convenient means for identifying discreteactivities or ingredients and the recited lettering can be arranged inany sequence, unless otherwise indicated.

As used herein the term “and/or,” when used in a list of two or moreitems, means that any one of the listed items can be employed by itself,or any combination of two or more of the listed items can be employed.For example, if a composition is described as containing components A,B, and/or C, the composition can contain A alone; B alone; C alone; Aand B in combination; A and C in combination; B and C in combination; orA, B, and C in combination.

The term “fibers”, as used herein, refers to thin flexible threadlikeobjects. Fibers can be natural fibers or man-made. The term “polymer”,as used herein refers to the base material from which the fibers aremade. Non-limiting examples of polymers include acrylic, modacrylic,aramid, nylon, polyester, polypropylene, rayon, polyacrylonitrile,polyethylene, PTFE, and cellulose acetate. The term “filament”, as usedherein, refers to a single fiber. The term “fiber band”, as used herein,refers to multiple fibers placed adjacent to each other along theirlengths such that the fibers remain untwisted or entangled and form asubstantially rectangular cross section with a high width-to-depthratio. Fiber bands are often formed to allow for effective crimping ofthe fibers and can be cut into a staple or processed as a continuousband, depending on the end use. Fiber bands are typically not woven orknitted into a fabric article unless first converted into staple to forma thread. Fibers can also be in the form of yarn. The term “yarn”, asused herein, refers to multiple fibers placed adjacent to each otheralong their lengths, often twisted or entangled together to improvefiber cohesiveness and performance, and typically forming asubstantially rounded cross section. Yarn can be processed as continuousstrands or cut into smaller lengths, depending on the end use.

Fibers can be identification fibers and/or standard fibers. The term“standard fibers”, as used herein, refers to fibers which aremanufactured for the primary purpose and use in producing articles.Standard fibers have not been purposefully manipulated to comprisechemical markers used to identify and track the standard fibers, yarn, afiber band, and/or an article comprising standard fibers. The term“identification fibers”, as used herein, refers to the fibers havingchemical markers that can be used to identify and track the fibers,yarn, or fiber band. Identification fibers can be all of the fibers, oralternatively, identification fibers can be a subset of the fibers inthe fibers, yarn, or fiber band.

The term “chemical markers”, as used herein, refers to chemicalcompounds added to, or inherent in, the fibers for identificationpurposes. Non-limiting examples of chemical markers include non-volatileorganic compounds, photoluminescent materials, polymeric additives,carbohydrates, metal oxides, inorganic salts, optical isomers,isotopically labeled molecules, and trace chemicals inherent to themanufacturer of the fibers and/or fiber raw materials. The term “taggantchemical markers”, as used herein, refers to a collection of chemicalmarkers used by one or more entity (e.g., manufacturer) in a system forembedding and/or determining standard fibers, yarn, and/or fiber bandsupply chain information.

The term “chemical marker amount”, as used herein, refers to the amountof a chemical marker present in the fibers, yarn, fiber band, and/orarticle based on the weight of the fibers. The fibers can includeidentification fibers and/or standard fibers. The term of “taggantchemical marker amount”, as used herein, refers to the collection ofchemical marker amounts which can be used by one or more entity (e.g.,manufacturer) in a system for embedding and/or determining standardfibers, yarn, fiber band, and/or article supply chain information.

The term “photoluminescent materials” as used herein, refers to eitherphotoluminescent compounds or absorbent dyes. The concentration of thephotoluminescent may be so small as to not be observed by image analysisand yet be detectable via chemical analysis, for example, spectroscopy.

The term “isotopically labeled molecules”, as used herein, refers tomolecules synthesized with higher levels of stable isotopes thannormally found in nature. Non-limiting examples of stable isotopesinclude carbon (¹²C/¹³C), oxygen (¹⁶O/¹⁸O), sulfur (³²S/³⁴S) andnitrogen (¹⁴N/¹⁵N).

The term “trace chemicals inherent to the manufacture”, as used herein,refers to chemical markers incorporated into a product via, for example,raw materials or processing aids. The term “trace chemicals inherent tothe manufacture of polymer”, as used herein, refers to chemical markersincorporated into the polymer during the polymer manufacture via, forexample, raw materials or processing aids. The term “trace chemicalsinherent to the manufacture of fibers”, as used herein, refers tochemical markers incorporated into the fiber during the fibermanufacture via, for example, raw materials or processing aids. The term“trace chemicals inherent in the manufacture of a fiber band”, as usedherein, refers to chemical markers incorporated into the fiber bandduring the fiber band manufacture via, for example, raw materials orprocessing aids.

The term, “polymer”, as used herein, refers to the resin or materialused to make the fiber. The polymer can comprise synthetic or naturalmaterial. The term “average molecular weight”, as used herein, refers tothe number or weight average molecular weight of a polymer or polymericadditive. The term “spinning solvent”, as used herein, refers to thematerial in which a polymer can be solubilized, wherein the solution ofpolymer and spinning solvents can be extruded into a fiber.

The term “majority of fibers”, as used herein, refers to greater than 50percent of the fibers in the yarn or fiber band based on the totalnumber of fibers.

The term, “cellulose acetate”, as used herein, refers to an acetateester of cellulose wherein the hydrogen in the hydroxyl groups of thecellulose glucose unit is replaced by acetyl groups through anacetylation reaction. In some embodiments, suitable cellulose acetatesmay have a degree of substitution less than about 3 acetyl groups perglucose unite, preferably in the range of 2.2 to about 2.8, and mostpreferably in the range of 2.4 to 2.7.

The terms, “cellulose acetate tow” or “acetate tow”, as used herein,refers to a continuous, crimped fiber band comprised of celluloseacetate fibers. The term “cellulose acetate yarn, as used herein, refersto a continuous uncrimped fiber band comprised of cellulose acetatefibers.

The term, “article”, as used herein, refers to a unit produced fromstandard fibers, yarn, and/or a fiber band, including other componentsand additives needed to meet the functional requirements of the intendeduse. Non-limiting examples include, fabrics and other textile products,non-wovens, absorbent products, filters, filter rods, cigarette filtersand liquid storage reservoirs. The term “article comprising fibers,yarn, or fiber bands”, as used herein, refers to the article comprisingthe fibers, yarn, or fiber bands with a recognition that, in someembodiments, significant physical changes can occur to the fibers, yarn,or fiber band when it is used to make an article.

The term, “filter”, as used herein refers to a semi-permeable fibrousmaterial. Non-limiting examples of filters include a filter rod, anditems made from a filter rod such as a cigarette filter. The term“filter rod”, as used herein, refers to a cylindrical article, of anycross-sectional shape, produced from a fiber band and other componentsor additives, which can be subsequently used as a whole unit, or cutinto lengths to form multiple units, for filtration of a vapor stream.Filter rods can be used to filter tobacco products, for example,traditional cigarette filters and/or other applications for othertobacco products including heat-not-burn products. Filter rods can alsobe used for new products comprising tobacco and other ingredients suchas, for example, other plants or plant derivatives. Filter rods can beused to filter other plants and plant derivatives, with or withouttobacco present. Additionally filter rods can be used to filter anyvapor stream used to deliver an active ingredient such as ine-cigarette.

The term, “cigarette filter”, as used herein, refers to a component ofthe cigarette or other smoking device which removes or decreases one ormore elements from a smoke stream. The term cigarette filter is intendedto encompass the filter on any smoking device including the non-limitingexamples of a cigarette, a cigarette holder, a cigar, a cigar holder, apipe, a water pipe, a hookah, an electronic smoking device, aroll-your-own cigarette, a roll-your-own cigar, cigarette filter tube,and heat-not-burn cigarettes.

The term, “supply chain information” as used herein, refers toinformation regarding the production of the standard fibers, yarn,and/or fiber band and information regarding the distribution of thestandard fibers, yarn, and/or fiber band after its production. Supplychain information includes “supply chain components” such as, forexample, manufacturer, manufacture site, manufacture line, productionrun, production date, package, bale, customer, customer ship-tolocation, warehouses, freight carrier, and/or shipment paths or routes.Supply chain components can apply to fibers, yarn, fiber bands, and/orarticles.

The term, “manufacturer”, as used herein, refers to the entity thatproduces the standard fibers, yarn, and/or fiber band.

The term “manufacture site”, as used herein, refers to the geographiclocation or locations of the manufacturer, designated by any level ofspecificity including full address, continent, country, state, province,county, or city.

The term “manufacture line”, as used herein, refers to specific processequipment or set of equipment used by the manufacturer to produce thestandard fibers, yarn, and/or fiber band.

The term “production run”, as used herein, refers to a group or set ofsimilar or related goods that are produced by using a particular set ofmanufacturing procedures, processes, or conditions, and/or productspecifications.

The term “customer”, as used herein, refers to an entity to which thefibers, yarn, or fiber band is sold and shipped for further processinginto an intermediate article or a finished product article; or an entitythat purchases the yarn or fiber band for resale.

The term, “ship-to location”, as used herein, refers to the geographiclocation of the customer designated for delivery of the fibers, yarn, orfiber band by any level of specificity including full address,continent, country, state, province, county, or city.

The term, “bale” as used herein, refers to a packaged unit of fiberbands, typically of a cubical shape, compressed to a high density, andwrapped, contained, and protected by packaging material.

The term, “warehouse” as used herein, refers to the geographicallocation of the warehouse designated for delivery of the fibers, yarn,or fiber band by any level of specificity including full address,continent, country, state, province, country, or city.

The term, “correlating”, as used herein refers to establishing therelationship between two or more pieces of information.

The term, “manufacturer specific taggants”, as used herein, refers tothe particular taggants incorporated into fibers, a yarn, or a fiberband by a particular manufacturer. The term, “manufacturer specifictaggant set” refers to the taggant chemical markers associated with aparticular manufacturer.

The term, “fibers are produced”, “producing fibers”, and “fiberproduction process”, as used herein, refers to the process steps ofspinning fibers up through the gathering of the fibers into fiber bands.

The term, “identification fibers are packaged”, as used herein, refersto the process steps of transferring identification fibers from thespinning machine and packaging the identification fibers, for example,onto a spool or into a bale. The identification fibers wouldsubsequently need to be removed from the package in order to beincorporated into fibers, a yarn, or a fiber band comprising standardfibers.

The term, “spinning solution”, as used herein, refers to the material tobe spun. Non-limiting examples of a spinning solution can be a melt ofthe polymer for melt spinning or the fiber material dissolved in asolvent for dry or wet spinning.

The term, “crimper coolants”, as used herein, refers to liquids appliedto the fiber band at the crimper for the purpose of mitigating the heatcaused by friction and/or improving processability.

The term, “chemical analysis”, as used herein, refers to the equipmentand techniques used to identify and/or characterize chemical substances.

Fibers, yarns, or a fiber band comprises individual fibers. The materialfrom which the fibers are made is not particularly limiting. The fiberscan comprise, for example, acrylic, modacrylic, aramid, nylon,polyester, polypropylene, rayon, polyacrylonitrile, polyethylene, PTFE,or cellulose acetate. In one aspect, the fibers comprise celluloseacetates, cellulose triacetates, cellulose propionates, cellulosebutyrates, cellulose acetate-propionates, cellulose acetate-butyrates,cellulose propionate-butyrates, cellulose acetate-phthalates, starchacetates, acrylonitriles, vinyl chlorides, vinyl esters, vinyl ethers,and the like, any derivative thereof, any copolymer thereof, and anycombination thereof. In one aspect, the fibers comprise celluloseacetate. In one aspect, the fibers comprise natural fibers such as, forexample, cotton, hemp, and silk.

The fibers, yarn, or fiber band comprises one or more identificationfibers and standard fibers. Fibers are typically produced from apolymer. In one aspect, one or more of the identification fiberscomprise the same polymer as the standard fibers in the fibers, yarn, orfiber band. In another aspect, one or more of the identification fiberscomprise a different material than the standard fibers in the fibers,yarn, or fiber band.

The size of the individual fibers is not particularly limiting. The sizecan be given in terms of effective diameter, and in one aspect, theeffective diameter of the fibers range from, for example, 0.1 μm to 1000μm, 1 μm to 500 μm, 1 μm to 100 μm, 1 μm to 30 μm, 10 μm to 1000 μm, 10μm to 500 μm, 10 μm to 100 μm, 10 μm to 30 μm. In one aspect, the fiberscomprise cellulose acetate for which size is often given in terms ofdenier per filament (dpf) which is defined as the weight, in grams, of asingle filament 9000 meters in length. In one aspect, the size of thefibers ranges from 0.5 to 1000 dpf; 0.5 to 500 dpf; 0.5 to 100; 0.5 to 5dpf; 0.5 to 30 dpf; 0.5 to 10 dpf; 1 to 1000 dpf; 1 to 500 dpf; 1 to100; 1 to 5 dpf; 1 to 30 dpf; 1 to 10 dpf. In one aspect, the dpf of thefibers ranges from, for example, 1 to 30 dpf, 1 to 20 dpf, 1 to 10 dpf,2 to 30 dpf, 2 to 20 dpf, or 2 to 10 dpf.

The number of fibers making up a fibers, yarn, or fiber band is notparticularly limiting. In one aspect, the number of fibers in a yarn orfiber band may range from 10 to 50,000. In other non-limiting examples,the number of fibers in a yarn or fiber band ranges from 10 to 40,000;10 to 30,000; 10 to 20,000; 10 to 10,000; 10 to 1000; 100 to 50,000; 100to 40,000; 100 to 30,000; 100 to 20,000; 100 to 10,000; 100 to 1000; 200to 50,000; 200 to 40,000; 200 to 30,000; 200 to 20,000; 200 to 10,000;200 to 1000; 1000 to 50,000; 1000 to 40,000; 1000 to 30,000; 1000 to20,000; 1000 to 10,000; 5000 to 50,000; 5000 to 40,000; 5000 to 30,000;5000 to 20,000; 5000 to 10,000; 10,000 to 50,000; 10,000 to 40,000;10,000 to 30,000; or 10,000 to 20,000.

The fibers, yarn, or fiber band comprises fibers, wherein the fiberscomprise one or more identification fibers wherein the identificationfibers comprise 1 to 100 chemical markers. In other aspects, the numberof chemical markers ranges from 1 to 50, 1 to 20, 1 to 15, or 1 to 10,or 1 to 5, or 1 to 3.

In one aspect, essentially all of the fibers in the yarn or fiber bandare identification fibers. In this aspect, the identification fibers canbe distinguishable from fibers in a different yarn or fiber band. Inanother aspect, one or more identification fibers are distinguishablefrom the majority of fibers in the same yarn or fiber band. In yetanother aspect, the number of identification fibers ranges from 0.001 to100 percent of the fibers; or 0.01 to 50 percent of the fibers; or 0.01to 25 percent of the fibers; or 0.01 to 10 percent of the fibers; or0.01 to 5 percent of the fibers; or 0.01 to 1 percent of the fibers,each based on the total number of fibers. In another aspect, the numberof identification fibers ranges from 0.01 to 100 percent of the fibers;or 1 to 100 percent of the fibers; or 25 to 100 percent of the fibers;or 50 to 100 percent of the fibers; or 30 to 80 percent of the fibers.

In one aspect, unique chemical markers are used to tag fiber products.The chemical markers can be manipulated to provide unique code.Different types of chemical markers can be applied in different amountsto increase the number of unique codes available. Additionally chemicalmarkers can be combined with unique fiber physical structures to furtherincrease variables for unique codes.

The identification fibers comprise chemical markers. In one aspect, thechemical markers can include non-volatile organic compounds,photoluminescent materials, polymeric additives, carbohydrates, metaloxides, inorganic salts, optical isomers, isotopically labeledmolecules, and/or trace chemicals inherent to the manufacturer of thefiber band, the fibers and/or the polymer which is produced into thefibers. In one aspect, the chemical markers can include one or moretaggant non-volatile organic compounds, one or more taggantphotoluminescent materials, one or more taggant polymeric additives, oneor more taggant carbohydrates, one or more taggant metal oxides, one ormore taggant inorganic salts, one or more taggant optical isomers, oneor more taggant isotopically labeled molecules, and one or more tagganttrace chemicals inherent to the manufacturer of the fiber band, thefibers, and/or the polymer.

In one aspect, non-volatile organic compounds can be used as a taggant.In one aspect, one or more of the chemical markers comprise one or moretaggant nonvolatile organic compounds. In one aspect the number oftaggant non-volatile compounds ranges from 1 to 50, 1 to 25, 1 to 10, 1to 5, or 1 to 3. In one aspect, the taggant nonvolatile organiccompounds can comprise fatty acids. In one aspect, the taggantnonvolatile organic compounds can comprise lauric acid, palmitic acid,or stearic acid.

In one aspect, photoluminescent materials can be used as a taggant. Inone aspect, one or more of the chemical markers comprise one or moretaggant photoluminescent materials. In one aspect the number of taggantphotoluminescent materials ranges from 1 to 50, 1 to 25, 1 to 10, 1 to5, or 1 to 3. Non-limiting examples of photoluminescent materialsinclude organic dyes, organometallic phosphorescent compounds, inorganicfluorescent/phosphorescent molecules, organic fluorescent molecules,inorganic quantum dots, organic quantum dots. In one aspect, the taggantphotoluminescent materials comprise phosphorescent quantum dots. In oneaspect, the phosphorescent quantum dots comprise Cd/Se ligand stabilizedfluorescent nano-crystals.

In one aspect, polymeric additives can be used as a taggant. In oneaspect, one or more chemical markers comprise one or more taggantpolymeric additives. In one aspect, the number of taggant polymericadditives ranges from 1 to 50, 1 to 5, 1 to 10, 1 to 5, or 1 to 3. Thetaggant polymeric additives can be identified based on polymeric contentand/or molecular weight. In one aspect, one or more taggant polymericadditives comprises the polymer from which the fibers are produced. Inthis aspect, the taggant polymeric additive is distinguishable basedupon the differences in molecular weight. In one aspect, one or moretaggant polymeric additives are soluble in the spinning solution. In oneaspect, taggant polymeric additives comprise polystyrene with an averagemolecular weight ranging from 500 to 20,000,000. In other aspects,taggant polymeric additives comprise polystyrene with an averagemolecular weight ranging from 500 to 500,000, or 1,000 to 100,000.

In one aspect, carbohydrates can be used as a taggant. In one aspect,one or more of the chemical markers comprise one or more taggantcarbohydrates. In one aspect, the number of taggant carbohydrates rangesfrom 50 to 1, 25 to 1, 10 to 1, 5 to 1, or 3 to 1. One or more taggantcarbohydrates can comprise, for example, glucose, fructose, sucrose,and/or lactose.

In one aspect, metal oxides can be used as a taggant. In one aspect, oneor more of the chemical markers comprise one or more taggant metaloxides. In one aspect, the number of taggant metal oxides ranges from 1to 50, 1 to 25, 1 to 10, 1 to 5, or 1 to 3. One or more taggant metaloxides can comprise, for example, titanium dioxide, zirconium oxides,zinc oxides, aluminum oxides, manganese oxides, magnesium oxides,calcium oxides, tin oxides, vanadium oxides, nickel oxides and/or ironoxides. In another example, one or more taggant metal oxides cancomprise titanium dioxide and/or zinc oxides.

In one aspect, inorganic salts can be used as a taggant. In one aspect,one or more chemical markers can comprise one or more taggant inorganicsalts. In one aspect, the number of taggant inorganic salts ranges from1 to 50, 1 to 25, 1 to 10, 1 to 5, or 1 to 3. Non-limiting examples oftaggant inorganic salts include lithium, sodium, potassium, magnesium,and/or calcium. In one aspect, the taggant inorganic salts comprisesalts of cesium, indium, or samarium.

In one aspect, optical isomers can be used as a taggant. In one aspect,one or more chemical markers can comprise one or more taggant opticalisomers. In one aspect, the number of taggant optical isomers rangesfrom 1 to 50, 1 to 25, 1 to 10, 1 to 5, or 1 to 3.

In one aspect, isotopically labeled molecules can be used as thetaggant. In one aspect, one or more chemical markers can comprise one ormore taggant isotopically labeled molecules. In one aspect, the numberof taggant isotopically labeled molecules ranges from 1 to 50, 1 to 25,1 to 10, 1 to 5, or 1 to 3. One skilled in the art recognizes that, forexample, ¹⁴C or ¹⁸O can be inserted into molecules that can be added tothe polymer, the fibers, or the fiber band.

In one aspect, trace chemicals inherent to the manufacture of the fiberband, fibers, and/or polymer can be used as a taggant. In one aspect,one or more of the chemical markers comprise one or more taggant tracechemicals. In one aspect, the number of taggant trace chemicals rangesfrom 1 to 50, 1 to 25, 1 to 10, 1 to 5, or 1 to 3. In one aspect, one ormore taggant trace chemicals are incorporated into the fibers, yarn, orfiber band through the polymer, a spinning solvent, utilities (e.g.,water, plant nitrogen), and/or processing aids.

In one aspect, the amount of one or more chemical markers ranges from 1ppb to 10,000 ppm of the fibers. In other examples, the amount of one ormore chemical markers ranges from 1 ppb to 5000 ppm; 1 ppb to 1000 ppm;1 ppb to 500 ppm; 1 ppb to 100 ppm; 1 ppb to 10 ppm; 1 ppb to 1 ppm; 1ppb to 500 ppb; 1 ppb to 100 ppb; 10 ppb to 10,000 ppm; 10 ppb to 5000ppm; 10 ppb to 1000 ppm; 10 ppb to 500 ppm; 10 ppb to 100 ppm; 10 ppb to10 ppm; 10 ppb to 1 ppm; 10 ppb to 500 ppb; 10 ppb to 100 ppb; 100 ppbto 10,000 ppm; 100 ppb to 5000 ppm; 100 ppb to 1000 ppm; 100 ppb to 500ppm; 100 ppb to 100 ppm; 100 ppb to 10 ppm; 100 ppb to 1 ppm; 100 ppb to500 ppb; 500 ppb to 10,000 ppm; 500 ppb to 5000 ppm; 500 ppb to 1000ppm; 500 ppb to 500 ppm; 500 ppb to 100 ppm; 500 ppb to 10 ppm; 500 ppbto 1 ppm; 1 ppm to 10,000 ppm; 1 ppm to 5000 ppm; 1 ppm to 1000 ppm; 1ppm to 500 ppm; 1 ppm to 100 ppm; 1 ppm to 10 ppm; 10 ppm to 10,000 ppm;10 ppm to 5000 ppm; 10 ppm to 1000 ppm; 10 ppm to 500 ppm; 10 ppm to 100ppm; 100 ppm to 10,000 ppm; 100 ppm to 5000 ppm; 100 ppm to 1000 ppm;and/or 100 ppm to 500 ppm of the fibers.

An article can comprise the fibers, yarn, or fiber band. The article isnot particularly limited. Non-limiting examples of articles comprisingthe fibers, yarn, or the fiber band include fabrics and other textileproducts, non-wovens, absorbent products, filters, filter rods,cigarette filters, liquid storage reservoirs, paper and/or currency. Inone aspect, the article comprises a filter rod. In another aspect, thearticle comprises a cigarette filter. In one aspect, the articlecomprises a medical device such as a medical cloth or bandage. Inanother aspect, the article comprises a wicking device.

In one aspect, one or more of chemical marker amounts corresponds to ataggant chemical marker amounts. In other words, for particular chemicalmarker, a specific amount of chemical marker (a taggant chemical markeramount) is included in the fibers. One skilled in the art recognizesthat the measured chemical marker amount and the taggant chemical markeramount may not be exactly the same due to measurement and other sourcesof variability. Therefore, “chemical marker amount corresponds to ataggant chemical marker amount” means that the chemical marker amount issufficiently close to indicate the presence of the taggant chemicalmarker amount. The taggant chemical marker amounts for each of thechemical markers can be selected from all of the chemical marker amountslisted above. Also, the number of taggant chemical marker amounts can bethe same or different for each chemical marker amount. The number oftaggant chemical marker amounts is selected, in part, based upon theability to manufacture and reliably detect discrete amounts of each ofthe chemical markers. In one aspect, the number of taggant chemicalmarkers ranges from 1 to 25, 1 to 15, 1 to 10, 1 to 5, 2 to 20, 2 to 15,2 to 10, 3 to 20, 3 to 15, 3 to 10, 4 to 20, 4 to 15, or 4 to 10.

In one aspect, the fibers, yarn, or fiber band has determinable supplychain information. The supply chain information can includemanufacturer, manufacture site, manufacturing line, production run,production date, bale, warehouse, customer, and/or ship-to location. Thetype taggant chemical marker and/or taggant chemical marker amounts canbe correlated to manufacturer-specific taggants to determine supplychain information of the fibers, yarn, fiber band, and/or article.

In one aspect, at least one supply chain component comprises amanufacturer of the standard fibers, a manufacture site of the standardfibers, a manufacturing line of the standard fibers, a production run ofthe standard fibers, a production date of the standard fibers, a packageof the standard fibers, a warehouse of the standard fibers, a customerof the standard fibers, a ship-to location of the standard fibers, amanufacturer of a yarn or fiber band comprising the standard fibers, amanufacturing site of the yarn or fiber band, a manufacturing line ofthe yarn or fiber band, a production run of the yarn or fiber band, aproduction date of the yarn or fiber band, a package of the yarn orfiber band, a warehouse of the yarn or fiber band, a customer of theyarn or fiber band, a ship-to location of the yarn or fiber band, amanufacturer of an article comprising the standard fibers, a manufacturesite of the article, a manufacturing line of the article, a productionrun of the article, a production date of the article, a package of thearticle, a warehouse of the article, a customer of the article, or aship-to location of the article.

In another aspect, the supply chain information comprises themanufacturer of the fiber band. In one aspect, the supply chaininformation comprises the manufacture site of the fiber band. In oneaspect the supply chain information comprises the manufacturing line ofthe fiber band. The manufacturing line of the fiber band is themanufacturing line on which the fiber band was produced. In one aspect,the supply chain information comprises the production run of the fiberband. The production run of the fiber band is the production run withinwhich the fiber band was produced. In one aspect, the supply chaininformation comprises the production date of the fiber band. Theproduction date of the fiber band is the production date on which thefiber band was produced. In one aspect, the supply chain informationcomprises the bale of the fiber band. In one aspect, the supply chaininformation comprises the customer of the fiber band. The customer ofthe fiber band is the customer to whom the manufacturer plans to send orhas sent the fiber band. In one aspect, the supply chain informationcomprises the ship-to location of the fiber band. The ship-to locationof the fiber band is the specific geographic location to which themanufacturer plans to send or has sent the fiber band.

The selection of the chemical markers, taggant chemical marker amounts,number of the taggant chemical marker amounts for each of the chemicalmakers, and coding system can be influenced by several factors. Thesefactors include, but are not limited to, ease of manufacturingidentification fibers, yarn, and/or fiber bands comprisingidentification fibers; ease of detecting identification fibers, eitherin the fibers, yarn, the fiber band, or in an article comprising thefibers, yarn or the fiber band; impact of the identification fibers onperformance characteristics of an article comprising the fibers, yarn,or the fiber band; and ease of countering the track and trace objective.

The disclosed embodiments allow for flexible implementation of a codingsystem for correlating the chemical markers, taggant chemical markeramounts, number of the taggant chemical marker amounts for each of thechemical makers. Described below are non-limiting examples of how codingsystems can be readily implemented based upon the above describedidentification fibers.

In a non-limiting example of using chemical markers for a particularcoding system, three chemical markers, lauric acid, palmitic acid, andstearic acid are the taggant non-volatile organic compounds. If, lauricacid can be present in the fibers in an amount of 1 wt %, 5 wt % or 10wt %, palmitic acid can be present at 100 ppm, or 200 ppm, and stearicacid can be present at 0.5 wt %, 1 wt %, 2 wt % or 4 wt %, then thereare 3 taggant lauric acid amounts, 2 taggant palmitic acid amounts, and4 taggant stearic acid amounts. If the coding system requires each oflauric acid, palmitic acid, and stearic acid to be present, there are 48different combinations of chemical markers and taggant chemical markeramounts. Each combination could be representative of a supply chaincomponent.

Another non-limiting example of correlating chemical markers, taggantchemical marker amounts, number of the taggant chemical marker amountsfor each of the chemical makers in a coding system includes a fiber bandhaving identification fiber(s) with a taggant fluorescent chromophore(as the taggant photoluminescent material) having a maximum emissionswavelength (λ_(max)) obtained from the emission spectrum of thedissolved fiber band. The λ_(max) of the taggant correlates to a number,0-9, which is used to identify the manufacturer. The taggant fluorescentchromophore amount correlates to a number, 0-9, which is used toidentify the manufacture site. Additionally, the fiber band includesidentification fibers with a taggant non-volatile compound whosemolecular constituents are determined and correlates to a number, 00-99,which is used to identify the customer. The taggant non-volatilecompound amounts is determined and correlates to a number, 00-99, whichis used to identify the ship-to location. The identity and quantity ofthe taggant non-volatile organic compound is determined using ananalytical technique such as GC or HPLC. Such a code could be 1 3 48 39which when compared to a database identifies the manufacturer and themanufacture site of the fiber band as well as the customer to which thefiber band is being sold, and the ship-to location. Other chemicalmarkers may be incorporated to encode additional information.

In additional embodiments, an acetate tow band comprises fibers,comprising standard fibers and identification fibers. The standardfibers comprise cellulose acetate. The identification fibers comprise 1to 20 chemical markers. The amount of each of the chemical markers,based on a weight of the fibers, is defined as a chemical marker amount.The chemical markers and the chemical marker amounts are representativeof at least one supply chain component of the acetate tow band.

The acetate tow band of the second embodiment encompasses acetate towbands comprising fibers with any combination of attributes describedabove. Specifically, the identification fiber composition, the sizes andnumbers of fibers, the percentage of identification fibers in fibers,yarn, or fiber band, the chemical markers including non-volatile organiccompounds, photoluminescent materials, polymeric additives,carbohydrates, metal oxides, inorganic salts, optical isomers,isotopically labeled molecules, and trace chemicals inherent to themanufacturer of the fibers and/or fiber raw materials, the chemicalmarker amounts, the taggant chemical marker amounts, the supply chaininformation, and the non-limiting coding/correlation systems apply tothe acetate tow band of the second embodiment.

In one aspect, the identification fibers comprise cellulose acetate. Inone aspect, the at least one supply chain component comprises themanufacturer of the acetate tow band and the customer of the acetate towband. In one aspect, the at least one supply chain component comprisesthe manufacturer of the acetate tow band and the ship-to location of theacetate tow band.

The number of chemical taggants that can be used is nearly limitless.Some considerations when selecting a taggant to use in acetate towconverted to cigarette filters include being non-toxic, approved forfood use (GRAS—generally regarded as safe), not providing adverse tastesor sensory changes, not interfering with the processing of the tow, andbeing readily analyzable using conventional laboratory methods.

Because cellulose acetate tow is made on an industrial scale, it isamenable to being tagged with various components to identify themanufacturer, as well as other supply chain information such as thecustomer it was sold to, location of shipment, or even a uniqueidentifier, i.e., a serial number, for each bale of tow.

The disclosed embodiments also include a filter comprising the acetatetow band described above. In one aspect the filter comprises a filterrod or a cigarette filter.

A third disclosed embodiment provides a method for making an acetate towband comprising fibers, comprising standard fibers and identificationfibers. The standard fibers comprise cellulose acetate. The methodcomprises (a) obtaining the identification fibers, wherein theidentification fibers comprise 1 to 20 chemical markers; (b) producingthe standard fibers on a first fiber production process; and (c)combining the standard fibers with the identification fibers into theacetate tow band. The amount of each of the chemical markers, based on aweight of the fibers, is defined as a chemical marker amount. Thechemical markers and the chemical marker amounts are representative ofat least one supply chain component of the acetate tow band.

The method for making a yarn or fiber band, such as an acetate tow band,encompasses making a yarn or fiber band comprising the fibers with anycombination of attributes disclosed above. Specifically, theidentification fiber composition, the sizes and numbers of fibers, thepercentage of identification fibers in fibers, yarn, or fiber band, thechemical markers including non-volatile organic compounds,photoluminescent materials. polymeric additives, carbohydrates, metaloxides, inorganic salts, optical isomers, isotopically labeledmolecules, and trace chemicals inherent to the manufacturer of thefibers and/or fiber raw materials, the chemical marker amounts, thetaggant chemical marker amounts, the supply chain information, and thenon-limiting coding/correlation systems apply to the acetate tow band ofthe second embodiment given above apply equally well to the method formaking a fiber band.

In one aspect, at least a portion of the standard fibers are produced ona fiber production process. In another aspect, standard fibers arereceived from a third party. Obtaining the identification fiberscomprises at least one of (i) producing at least a portion of theidentification fibers on the standard fibers' fiber production process,(ii) producing at least a portion of the identification fibers on aprocess distinct from the standard fibers' fiber production process, or(iii) receiving at least a portion of the identification fibers from athird party.

In one aspect, the identification fibers are coproduced with thestandard fibers and all of the fibers making up a yarn or fiber band arecombined directly downstream of the fiber production process.

In another aspect, the identification fibers are produced and packagedseparately from standard fibers and the identification fibers arecombined with the standard fibers to produce a fiber band. The standardfibers may also have been packaged before combining with theidentification fibers, or the identification fibers may be combined withthe standard fibers before packaging of the fiber band.

The spinning process used for producing the fibers is not particularlylimited. In one aspect, the fibers are produced using dry spinning,solution spinning, melt spinning, electro spinning, gel spinning,multi-component spinning, melt blowing, and/or solution blowing. Inanother aspect, the fibers are produced using dry spinning, solutionspinning, melt spinning, electro spinning, gel spinning, and/ormulti-component spinning. In a further aspect, the fibers comprisecellulose acetate and are produced using dry spinning.

In one aspect, one or more chemical markers are selected from the groupconsisting of one or more taggant non-volatile organic compounds, one ormore taggant photoluminescent materials, one or more taggant polymericadditives, one or more taggant carbohydrates, one or more taggant metaloxides, one or more taggant inorganic salts, one or more taggant opticalisomers, one or more taggant isotopically labeled molecules and one ormore taggant trace chemicals inherent to the manufacturer of said fiberband, said fibers and/or said polymer.

In one aspect, the amount of one or more chemical markers (i.e. chemicalmarker amounts) ranges from 1 ppb to 10,000 ppm; 1 ppb to 5000 ppm; 1ppb to 1000 ppm; 1 ppb to 500 ppm; 1 ppb to 100 ppm; 1 ppb to 10 ppm; 1ppb to 1 ppm; 1 ppb to 500 ppb; 1 ppb to 100 ppb; 10 ppb to 10,000 ppm;10 ppb to 5000 ppm; 10 ppb to 1000 ppm; 10 ppb to 500 ppm; 10 ppb to 100ppm; 10 ppb to 10 ppm; 10 ppb to 1 ppm; 10 ppb to 500 ppb; 10 ppb to 100ppb; 100 ppb to 10,000 ppm; 100 ppb to 5000 ppm; 100 ppb to 1000 ppm;100 ppb to 500 ppm; 100 ppb to 100 ppm; 100 ppb to 10 ppm; 100 ppb to 1ppm; 100 ppb to 500 ppb; 500 ppb to 10,000 ppm; 500 ppb to 5000 ppm; 500ppb to 1000 ppm; 500 ppb to 500 ppm; 500 ppb to 100 ppm; 500 ppb to 10ppm; 500 ppb to 1 ppm; 1 ppm to 10,000 ppm; 1 ppm to 5000 ppm; 1 ppm to1000 ppm; 1 ppm to 500 ppm; 1 ppm to 100 ppm; 1 ppm to 10 ppm; 10 ppm to10,000 ppm; 10 ppm to 5000 ppm; 10 ppm to 1000 ppm; 10 ppm to 500 ppm;10 ppm to 100 ppm; 100 ppm to 10,000 ppm; 100 ppm to 5000 ppm; 100 ppmto 1000 ppm; and/or 100 ppm to 500 ppm of said fibers.

The method for incorporating the chemical markers into the fiber band isnot particularly limited. Chemical markers disclosed herein can beincorporated in the cellulose acetate tow manufacturing process byseveral possible methods and at many steps or locations in the process.The general methods would include introduction and mixing in bulk whilethe product or its raw materials are in a liquid form (e.g. pigmentslurry; acid dope; acetone dope; acetic acid; acetic anhydride;neutralization agents; lubricant emulsion) or applied to the surface ofthe product when in solid form (e.g. pulp rolls; pigment granules;cellulose acetate flake; tow after spinning).

In one aspect, one or more chemical markers can be added to the polymerfrom which the identification fibers are made. In one aspect, thechemical marker is added to the spinning solution. The spinning solutionis subsequently spun into one or more identification fibers. Thechemical marker can be added to the spinning solution upstream of themanufacturing line to be incorporated into all of the fibers of thefiber band or upstream of one or more spinning cabinets or one or moreindividual spinnerets to incorporate the marker into a portion of thefibers of the fiber band. Static mixers can be used to mix the chemicalmarker in the spinning solution piping without mechanical agitation. Theaddition of the chemical markers at the cabinet or spinneret levelallows for quicker and less costly purging of the spinning system whenchemical marker changes are needed to represent a different supply chaincomponent, for example a different ship to location. In one aspect, oneor more of the chemical markers is added to a spinning solution upstreamof the first fiber production process, at a spinning cabinet containedwithin the first fiber production process, or at an individual spinneretcontained within the spinning cabinet.

In one aspect, chemical markers are applied to one or moreidentification fibers by surface application at any point before,during, and/or after the forming of the yarn or fiber band; before,during and/or after the crimping of the fiber band; before, duringand/or after the conditioning of the yarn or fiber band; before, duringand/or after the conveyance of the yarn or fiber band to the packagingprocess. In one aspect, the spin finish comprises one or more chemicalmarkers and is applied to the fiber through existing spin finishapplication equipment. In another aspect, the existing crimper coolantcomprises one or more chemical markers.

In one aspect chemical markers can be applied by surface application toone or more identification fibers by a method selected from the groupconsisting of dipping, immersing, submerging, soaking, rinsing, washing,painting, coating, showering, drizzling, spraying (as liquid oratomized), placing, dusting, sprinkling, affixing, pouring, and directmetering.

In addition to the flexibility of where and how chemical markers areadded to the process for making a yarn or fiber band, the form of thechemical markers is not particularly limited. In one aspect, chemicalmarkers can be applied in a form selected from the group consisting ofneat, in a solution, in an emulsion, and in a suspension.

The location at which the chemical markers are added may determine thedegree of differentiation possible within the supply chain information,e.g. manufacturing location, manufacturing line, production run, orbale. Generally the further upstream the chemical markers areincorporated, the less differentiation is possible. However, the furtherdownstream the chemical markers are applied, the greater the potentialcapital expense and manufacturing complexity due to the need for amultiplicity of equipment additions and modifications. In one aspect,one or more chemical markers can be added at the point of manufacture ofthe article. In one aspect, one or more chemical markers can be added atthe plugmaker when an acetate tow band is converted into a filter rod.

In one aspect, the identification fibers comprise cellulose acetate. Inone aspect, the at least one supply chain component comprises themanufacturer of the acetate tow band and the customer of the acetate towband. In one aspect, the at least one supply chain component comprisesthe manufacturer of the acetate tow band and the ship-to location of theacetate tow band.

The disclosed embodiments also provide a method for characterizing afiber sample comprising fibers. The fibers comprise standard fibers andidentification fibers. The identification fibers comprise 1 to 100chemical markers. The amount of each of the chemical markers, based on aweight of the fibers, is defined as a chemical marker amount. Thechemical markers and the chemical marker amounts are representative ofat least one supply chain component of the acetate tow band. The methodcomprises: (a) dissolving the fiber sample in a solvent to produce asample solution and/or insolubles; (b) analyzing the sample solutionand/or the insoluble to identify the chemical markers and the chemicalmarker amounts.

The method for characterizing a fiber sample encompasses characterizinga fiber sample comprising fibers, a yarn, fiber band, and/or articlecomprising the fibers with any combination of attributes disclosedabove. Specifically, the identification fiber composition, the sizes andnumbers of fibers, the percentage of identification fibers in a fibers,yarn, or fiber band, the chemical markers including non-volatile organiccompounds, photoluminescent materials, polymeric additives,carbohydrates, metal oxides, inorganic salts, optical isomers,isotopically labeled molecules, and trace chemicals inherent to themanufacturer of the fibers and/or fiber raw materials, the chemicalmarker amounts, the taggant chemical marker amounts, the supply chaininformation, and the non-limiting coding/correlation systems apply tothe method for characterizing a fiber sample. Additionally, the fiberband can be made using any combination of attributes disclosed above inthe method for making a fiber band.

In one aspect, the solvent is selected from the group consisting ofethers; ketones; aliphatic and aromatic hydrocarbons; water; and ionicliquids. In one aspect, the aliphatic and aromatic hydrocarbons comprisehetero atoms, wherein the heteroatoms comprise halogens, amines, oxygen,sulfur and/or phosphorus. In another aspect, the solvent comprisesacetone, tetrahydrofuran, dichloromethane, methanol, chloroform,dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl acetate,ethyl acetate, nitric acid and/or pyridine.

The equipment and techniques used to identify the chemical markers arenot particularly limited. One skilled in the art of analytical chemistrywill recognize that there are several chemical analysis technologiesuseful in analyzing articles and/or prepared samples, for example, bydissolving the articles in a solvent. In one aspect, the chemicalmarkers are analyzed using mass spectrometry, spectroscopy, nuclearmagnetic resonance, and/or x-ray diffraction. In one aspect, thechemical markers are analyzed using chromatography and/or inductivelycoupled plasma. One skilled in the art recognizes that these are broadcategories of chemical analysis technologies. The specific types of eachchemical analysis technology can be used in analyzing chemical markersin the fiber band.

In one aspect, the method for characterizing the fiber sample furthercomprises (a) correlating one or more of chemical markers and/orchemical marker amounts to a database comprising manufacturer-specifictaggants; and (b) determining supply chain information of the fibersample. The supply chain information can include manufacturer,manufacture site, manufacturing line, production run, production date,bale, warehouse, customer, and/or ship-to location.

In one aspect, the supply chain information comprises the manufacturerof the fiber band in the article. In one aspect, the supply chaininformation comprises the manufacture site of the fiber band in thearticle. In one aspect the supply chain information comprises themanufacturing line of the fiber band in the article. The manufacturingline of the fiber band is the manufacturing line on which the fiber bandwas produced. In one aspect, the supply chain information comprises theproduction run of the fiber band in the article. The production run ofthe fiber band is the production run within which the fiber band wasproduced. In one aspect, the supply chain information comprises theproduction date of the fiber band in the article. The production date ofthe fiber band is the production date on which the fiber band wasproduced. In one aspect, the supply chain information comprises the baleof the fiber band in the article. In one aspect, the supply chaininformation comprises the customer of the fiber band in the article. Thecustomer of the fiber band is the customer to whom the manufacturerplans to send or has sent the fiber band. In one aspect, the supplychain information comprises the ship-to location of the fiber band inthe article. The ship-to location of the fiber band is the specificgeographic location to which the manufacturer plans to send or has sentthe fiber band.

The disclosed embodiments also include the making an article with afiber band having any of the disclosed features. Additional disclosedembodiments also include an article comprising a fiber band having anyof the disclosed features. In other embodiments, the fibers having anyof the disclosed features are formed into a yarn.

In further embodiments, a method for embedding supply chain informationinto fibers includes obtaining standard fibers and obtainingidentification fibers. In one aspect, the identification fibers mayinclude one or more chemical markers, and each of the chemical markersmay be present within the identification fibers in a correspondingchemical marker amount. In further aspects, at least one of the chemicalmarker amounts may represent a taggant chemical marker amount. Themethod may also include combining the standard fibers with theidentification fibers. In certain aspects, the one or more chemicalmarkers and/or the at least one taggant chemical marker amount may berepresentative of at least one component of a supply chain.

In some aspects, at least a portion of the standard fibers, andadditionally or alternatively, at least a portion of the identificationfibers, may include cellulose acetate fibers. For example, the standardfibers may be combined with the identification fibers to form acellulose acetate tow band. Further, in some instances, a portion of atleast one of a filter rod or cigarette filter may be formed from thecellulose acetate tow band. In other aspects, the standard fibers may becombined with the identification fibers to form a portion of at leastone of fabrics, other textile products, non-wovens, and/or absorbentproducts.

The at least one supply chain component may include a manufacturer, amanufacture site, a manufacturing line, a production run, a productiondate, a bale, a warehouse, a customer, and/or a ship-to location. Forexample, the at least one supply chain component may represent amanufacturer of a portion of the standard fibers, and additionally oralternatively, a manufacturer of a portion of the identification fibers.

The method may also establish numbers of taggant chemical marker amountsfor the one or more chemical markers included within the identificationfibers. In some instances, the one or more chemical markers, the atleast one taggant chemical marker amount, and/or the established numbersof taggant chemical marker amounts may be representative of the at leastone component of a supply chain.

In one aspect, the method may receive, from a third party, informationidentifying (i) the one or more chemical markers, (ii) the at least onetaggant chemical marker amount, and/or (iii) the established numbers oftaggant chemical marker amounts.

In further aspects, the method may identify one or more proposedchemical markers, at least one proposed taggant chemical marker amount,and/or proposed numbers of taggant chemical marker amounts to representthe at least one component of the supply chain. The method may providethe one or more proposed chemical markers, the at least one proposedtaggant chemical marker amount, and/or the proposed numbers of taggantchemical marker amounts to a third party, and may receive, from thethird party, information indicative of an assignment of the one or moreproposed chemical markers, the at least one proposed taggant chemicalmarker amount, and/or the proposed numbers of taggant chemical markeramounts to the at least one component of the supply chain. In otheraspects, the method may assign the one or more proposed chemicalmarkers, the at least one proposed taggant chemical marker amount,and/or the proposed numbers of taggant chemical marker amounts to the atleast one component of the supply chain. The at least one component ofthe supply chain may, for example, correspond to a manufacturer.

The method may also generate correlation data mapping the one or morechemical markers, the at least one taggant chemical marker amount,and/or the numbers of taggant chemical marker amounts to the at leastone supply chain component. In certain instances, the method maygenerate the correlation data by mapping the one or more chemicalmarkers, the at least one taggant chemical marker amount, and/or numbersof taggant chemical marker amounts to the at least one supply chaincomponent.

In one aspect, the method may generate the correlation data bygenerating a first structured list of the supply chain components, andgenerating a second structured list of one or more chemical markersavailable for inclusion within the identification fibers. The method mayidentify taggant chemical marker amounts that are available forinclusion within the identification fibers, and may generate a thirdstructured list that includes combinations of the one or more availablechemical markers and the available taggant chemical marker amounts. Themethod may also include mapping elements of the first structured list toelements of the second structured list, and mapping elements of thefirst structured list to elements of the third structured list. Themethod may store correlation data reflecting the mapping of the elementsof the first and second structured lists and the mapping of the elementsof the first and third structured lists.

In other aspects, the method may generate the correlation data bygenerating a first structured list of the supply chain components, andgenerating a second structured list of one or more chemical markersavailable for inclusion within the identification fibers. The method mayalso generate a third structured list of numbers of taggant chemicalmarker amounts capable of representing supply chain components. Further,the method may map elements of the first structured list to elements ofthe second structured list, and map elements of the first structuredlist to elements of the third structured list. The method may storecorrelation data reflecting the mapping of the elements of the first andsecond structured lists and the mapping of the elements of the first andthird structured lists.

In one aspect, the method may obtain the standard fibers by producing atleast a portion of the standard fibers on a first fiber productionprocess. The first fiber production process may, for example, include adry-spinning process, a solution-spinning process, a melt-spinningprocess, an electro-spinning process, a gel-spinning process, amulti-component-spinning process, a melt-blowing process, and/or asolution-blowing process.

In additional aspects, the method may obtain the identification fibersby receiving at least a portion of the identification fibers from athird party and additionally or alternatively, by producing at least aportion of the identification fibers on a second fiber productionprocess. The second fiber production process may, for example, include adry-spinning process, a solution-spinning process, a melt-spinningprocess, an electro-spinning process, a gel-spinning process, amulti-component-spinning process, a melt-blowing process, and/or asolution-blowing process. In certain instances, the first productionprocess and the second fiber production process correspond to a commonfiber production process.

In some aspects, the method may produce the portion of theidentification fibers by receiving an indication of one or more supplychain components to reflect in the identification fibers; accessingstored correlation data; identifying, from the stored correlation data,one or more chemical markers and/or at least one taggant chemical markeramount mapped to the one or more selected supply chain informationcomponents; selecting at least one manufacturing method associated withproducing the identification fibers based on the one or more chemicalmarkers and/or the at least one taggant chemical marker amount; andproducing the identification fibers according to the selected at leastone manufacturing method.

In one aspect, the method may select the at least one manufacturingmethod by determining whether an introduction of the one or morechemical markers and/or at least one taggant chemical marker amount intothe identification fibers includes manipulating chemical properties ofthe identification fibers; identifying one or more manufacturing methodsfor the identification fibers based on the determination regardingintroduction of the one or more chemical markers and/or the at least onetaggant chemical marker amount into the identification fibers; andproducing the identification fibers according to the identified one ormore manufacturing methods.

The method may, for example, determine that the introduction of the oneor more chemical markers and/or the at least one taggant chemical markeramount into the identification fibers includes at least a manipulationof chemical properties. In response to the determination, the method mayidentify the one or more chemical markers for inclusion within theidentification fibers, and select at least one manufacturing methodcapable of producing the identification fibers with the identified oneor more chemical markers.

The one or more chemical markers may, for example, be selected from agroup consisting of one or more taggant non-volatile organic compounds,one or more taggant photoluminescent materials, one or more taggantpolymeric additives, one or more taggant carbohydrates, one or moretaggant metal oxides, one or more taggant inorganic salts, one or moretaggant optical isomers, one or more taggant isotopically labeledmolecules, or one or more taggant trace chemicals inherent to amanufacturer of the fiber band.

In some aspects, the at least one manufacturing method may include oneor more of applying the chemical markers to the identification fibers bya method selected from a group consisting of dipping, immersing,submerging, soaking, rinsing, washing, painting, coating, showering,drizzling, spraying as a liquid, spraying as an atomized substance,placing, dusting, sprinkling, affixing, pouring, or direct metering.

In further aspects, the at least one manufacturing method may includeapplying the one or more of chemical markers in a form selected from thegroup consisting of neat, in a solution, in an emulsion, and in asuspension. The at least one manufacturing may also include adding theone or more chemical markers to a spinning solution upstream of at leastone of a production line, spinning cabinets, or individual spinnerets.

In additional embodiments, a method for identifying supply chaininformation from fiber samples includes analyzing a fiber sample foridentification fibers. The method may identify one or more chemicalmarkers associated with the sample from the identification fibers, andmay determine a chemical marker amount associated with each of thechemical markers. In one aspect, the determined chemical marker amountsinclude at least one taggant chemical marker amount. The method mayaccess correlation data mapping components of a supply chain to the oneor more identified chemical markers and/or the at least one taggantchemical marker amount. Based on the accessed correlation data and theone or more identified chemical markers and/or the at least one taggantchemical marker amount, the method may identify at least one componentof the supply chain associated with the fiber sample.

In certain aspects, the fiber sample may include standard fibers and theidentification fibers, and the supply chain components may include amanufacturer, a manufacture site, a manufacturing line, a productionrun, a production date, a bale, a warehouse, a customer, and/or aship-to location. Further, by way of example, the at least oneidentified supply chain component may include a manufacturer, amanufacture site, a manufacturing line, a production run, a productiondate, a bale, a warehouse, a customer, and/or a ship-to location.

Further, for example, the fiber sample may include cellulose acetatefibers, and additionally or alternatively, may include a portion of acellulose acetate tow band. In other instances, the fiber sample mayinclude a portion of at least one of a filter rod or cigarette filter.The fiber sample may also include a portion of at least one of a textileproduct, a woven fabric, a non-woven fabric, or an absorbent product.

In some aspects, the method may receive a request to identify supplychain information associated with the fiber sample from a requestingentity, and may transmit information identifying the at least one supplychain component to the requesting entity. The requesting entity may, forexample, include a manufacturer, a customer, a governmental entity, alaw enforcement entity, and/or a third-party requestor.

In additional aspects, the method may identify a plurality of supplychain components based on the accessed correlation data and the one ormore identified chemical markers and/or the at least one taggantchemical marker amount, and may transmit information identifying asubset of the plurality of supply chain components to the requestingentity. Further, the method may also transmit, to the requesting entity,information identifying a manufacturer and additionally oralternatively, information identifying at least a portion of the one ormore identified chemical markers and/or the at least one taggantchemical marker amount.

In other aspects, the method may identify the one or more chemicalmarkers by selecting a solvent for conducting a chemical analysis;dissolving the sample in the selected solvent to produce a samplesolution; analyzing the sample solution; identifying the one or morechemical markers in the sample solution based on the analysis; andidentifying at least one measurable gradation for each of the one ormore identified chemical markers based on the analysis.

The method may determine that one or more fibers from the sample did notdissolve in the solvent. In response to the determination, the methodmay analyze the one or more undissolved fibers and identify at least oneobservable chemical marker based on the analysis.

In additional aspects, the method may analyze the one or moreundissolved fibers by selecting at least one additional solvent forconducting the chemical analysis, and dissolving at least one of theundissolved fibers in the at least one additional solvent to produce thesample solution. By way of example, the solvent and at least oneadditional solvent are selected from a group consisting of one or moreof ethers; ketones; aliphatic and aromatic hydrocarbons with or withoutheteroatoms comprising halogens, amines, oxygen, sulfur or phosphorus;water; or ionic liquids. In other instances, the solvent and at leastone additional solvent are selected from a group consisting of one ormore of acetone, tetrahydrofuran, dichloromethane, methanol, chloroform,dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl acetate,ethyl acetate, or pyridine.

The method may, in some aspects, analyze the sample solution using useof one or more of mass spectrometry, spectroscopy, nuclear magneticresonance, x-ray diffraction, or chromatography. Further, the method mayanalyze the sample solution by selecting at least one analysistechnique, characterizing each chemical marker from the one or moreidentified chemical markers according to the selected at least oneanalysis technique; identifying a concentration for each of the one ormore identified chemical markers; generating a deconvoluted spectrabased on the one or more characterized chemical markers and the one ormore identified concentrations; determining whether multiple chemicalmarkers are present among the one or more identified chemical markers;and determining whether non-volatile compounds are present in the samplesolution.

When the multiple chemical markers are determined to be present, themethod may further analyze sample solution by extracting a serial numberfrom the deconvoluted spectra. Additionally, when non-volatile compoundsare determined to be present, the method may further analyze the samplesolution by identifying molecular constituents of at least onenon-volatile compound present in the sample solution, and determining aquantity of each non-volatile compound from the at least onenon-volatile compound.

In certain exemplary embodiments described above, methods for embeddingsupply chain information obtain standard fibers and identificationfibers, and further, combine the obtained standard fibers with theobtained identification fibers for form fibers and/or fiber products.The disclosed embodiments are, however, not limited to methods combinestandard and identification fibers for form fibers and/or fiberproducts. In other embodiments, the exemplary methods outlined above mayembed supply chain information into fibers and/or fiber products thatinclude only identification fibers. For example, exemplary methods forembedding supply chain information into fibers may include obtainingidentification fibers that include one or more chemical markers. Each ofthe chemical markers may be present within the identification fibers ina corresponding chemical marker amount, and at least one of the chemicalmarker amounts may represent a taggant chemical marker amount. Incertain aspects, the obtained identification fibers may represent thefibers, which may be incorporated into a fiber product, and the one ormore chemical markers and/or the at least one taggant chemical markeramount may be representative of at least one component of a supplychain.

FIGS. 1A and 1B illustrate non-limiting examples of an environment 100depicting communication and shipping channels among entities consistentwith disclosed embodiments. In one embodiment, environment 100 of FIGS.1A and 1B may include one or more manufacturers 110, one or morecustomers 120, a black market 140 or other illicit trade network, one ormore requesting parties 130, one or more laboratories 160, andcommunication network 150. The components and arrangement of thecomponents included in environment 100 (e.g., as illustrated in FIGS. 1Aand 1B) may vary. Thus, environment 100 may include other componentsthat perform or assist in the performance of one or more processesconsistent with the disclosed embodiments.

In some aspects, network 150 may be any type of network configured toprovide communication means between systems of components of environment100 (e.g., manufacturing system 112 and/or laboratory system 162). Forexample, network 150 may be any type of network (includinginfrastructure) that facilitates communications, exchanges information,etc., such as the Internet, a Local Area Network, near fieldcommunication, and/or other suitable connection(s) that enables thesending and receiving of information between the component systemsassociated with environment 100. In other embodiments, one or morecomponent systems of environment 100 may communicate directly through adedicated communication link(s), such as links between manufacturer 110,customer 120, requesting party 130, and/or laboratory 160.

Further, and as stated above, manufacturers (e.g., manufacturer 110) mayproduce cellulose acetate fibers and fiber products that incorporate thecellulose acetate fibers on an industrial scale. In some embodiments,the produced cellulose acetate fibers and fiber products may includestandard fibers and identification fibers. The identification fibers mayinclude one or more chemical markers present in corresponding chemicalmarker amounts. Further, at least one of the chemical marker amounts mayrepresent a taggant chemical marker amount, which may distinguish theidentification fibers from the standard fibers. As stated above, the atleast one taggant chemical marker amount may be selected from a numberof taggant chemical marker amounts appropriate for inclusion within theidentification fibers. In certain aspects, the chemical markers, the atleast one taggant chemical marker amount, and/or the number of taggantchemical marker amounts may be representative of at least one supplychain component associated with fibers or fiber products, includingcellulose acetate fibers and fiber products.

In some embodiments, the inclusion of identification fibers in thecellulose acetate fibers may enable manufacturer 110 to tag thecellulose acetate fibers, and thus, the fiber products that include thecellulose acetate fibers, with supply chain information prior toshipment to customers 120. By way of example, fiber products consistentwith the disclosed embodiments may include, but are not limited to,cellulose acetate tow, loose bands of cellulose acetate tow, bales ofcellulose acetate tow, and fabrics and other articles that include thecellulose acetate fibers and/or tow.

For example, and in the context of cigarette manufacturing, customer 120may use a bale of acetate tow to produce various intermediate and/orfinal stage products (e.g., loose tow band, filter rods, filters, and/orcigarettes) and a fraction of these products can ultimately find theirway onto the black market (e.g., black market 140). Thus, because supplychain information can be determined from a sample of any black marketproduct having tagged identification fibers, a party interested incombating illicit trade (e.g., requesting party 130) may obtain a blackmarket product and submit a sample for analysis in order to identifysupply chain information associated with the black market product.

Thus, in one embodiment, requesting party 130 may provide the sample tomanufacturer 110, as depicted in FIG. 1A. Manufacturer 110 may, incertain aspects, analyze the sample to identify at least one componentof a supply chain associated with the sample. For example, the samplemay include standard and identification fibers, and in some instances,manufacturer 110 may analyze the sample using any of the exemplarytechniques outlined above.

Based on the analysis, manufacturer 110 may identify one or morechemical markers present within the identification fibers, and further,may identify at least one taggant chemical marker amount associated withone or more of the identified chemical markers. In certain aspects,manufacturer 110 may access correlation data mapping components of thesupply chain to the identified chemical markers and/or the at least oneidentified taggant chemical marker amount. Manufacturer 110 may identifythe at least one component of the supply chain based on, for example, acomparison of the identified chemical markers and/or the at least oneidentified taggant chemical marker amount to the accessed correlationdata. In some instances, manufacturer 110 may transmit informationidentifying the at least one supply chain component to requesting party130 (e.g., across network 150).

In the exemplary embodiments described above, manufacturer 110 mayanalyze the sample to identify at least one component of a supply chainassociated with the sample. The disclosed embodiments are, however, notlimited to exemplary analyses conducted by manufacturer 110, and infurther embodiments, customer 120, requesting party 130, or athird-party (not shown) may conduct the analysis for identifying supplychain information from tagged fibers.

For example, as illustrated in FIG. 1B, a laboratory 160 may act onbehalf of requesting party 130 and perform the analysis on the sample toidentify the at least one supply chain component associated with thesample. In some instances, laboratory 160 may represent a governmentalentity, a quasi-governmental entity, or a private entity capable ofperforming the analysis, and requesting party 130 may contract with orretain laboratory 160 to perform the analysis on a one-time or recurringbasis.

In other instances, however, laboratory 160 may be established by one ofmore of manufacturer 110, customers 120, and/or requesting party 130 inorder to regularly and reliably identify supply chain componentsassociated with samples taken from illicitly traded cellulose acetatefibers or fiber products that incorporate the cellulose acetate fibers(e.g., as obtained by requesting party 130 from black market 140).Laboratory 160 may, in certain aspects, perform the analysis of thesample in accordance with one or more procedures established by amanufacturer 110, customers 120, and/or requesting party 130. Forexample, one or more of manufacturer 110, customers 120, and/orrequesting party 130 may collectively establish standardized proceduresand protocols for receiving and handling samples, analyzing the samplesto identify the supply chain components in an accurate and repeatablemanner, and reporting portions of the identified supply chain componentsto manufacturer 110, customers 120, and/or requesting party 130.Further, in additional embodiments, laboratory 160 may also assign thechemical markers, the at least one taggant chemical marker amount, andadditionally or alternatively, the numbers of taggant chemical markeramounts to various components of the supply chain (e.g., manufacturers)to uniquely identify these supply chain components. In furtherembodiments, customer 120, requesting party 130, or a third-party (notshown) may assign a portion of the chemical markers, the at least onetaggant chemical marker amount, and/or the numbers of taggant chemicalmarker to various components of the supply chain (e.g., manufacturers)to uniquely identify these supply chain components.

In one embodiment, as illustrated in FIG. 1B, requesting party 130 mayprovide the sample to laboratory 160. Laboratory 160 may, in certainaspects, analyze the sample to identify at least one component of asupply chain associated with the sample (e.g., a manufacturer). Forexample, using any of the exemplary techniques described above,laboratory 160 may analyze the sample to identify chemical markers andfurther, at least one taggant chemical marker amount present within thesample. Further, laboratory 160 may access correlation data, and usingany of the exemplary techniques described above, identify the at leastone supply chain component based on a comparison of the chemical markersand/or the at least one taggant chemical marker amount to the accessedcorrelation data.

In additional embodiments, laboratory 160 may function as a centralizedfacility that assigns unique chemical markers, taggant chemical markeramounts, and/or numbers of taggant chemical marker amounts to variouscomponents of the supply chain (e.g., to manufacturer 110). For example,laboratory 160 may assign one or more chemical markers and at least onetaggant chemical marker amount to manufacturer 110.

When present in identification fibers included within cellulose acetatefibers and corresponding fiber products produced by manufacturer 110,the assigned chemical markers and/or at least one taggant chemicalmarker amount may uniquely represent manufacturer 110 and may enablelaboratory 160 (and additionally or alternatively, any other entitywithin environment 100) to identify manufacturer 110 as a source of thefiber products using any of the analytical techniques described above.Further, laboratory 160 (and additionally or alternatively, any otherentity within environment 100) may also establish and maintain datarecords (e.g., within a centralized database implemented using theexemplary computing systems outlined below) that identify a correlationbetween the various supply chain components (e.g., manufacturer 110) andthe assigned chemical markers and at least one taggant chemical markeramount (and additionally or alternative, one or more assigned numbers oftaggant chemical marker amounts).

In certain aspects, laboratory 160 may establish a centralizedrepository for data and data records (e.g., using any of the exemplarycomputing systems outlined below) that correlate the various supplychain components (e.g., manufacturer 110) to corresponding ones ofchemical markers, taggant chemical marker amounts, and/or numbers oftaggant chemical marker amounts. Further, in other aspects, laboratory160 may access the centralized repository and generate one or morereports specifying the chemical markers, taggant chemical markeramounts, and/or numbers of taggant chemical marker amounts that uniquelyidentify at least one of the supply chain components (e.g.,manufacturers). Laboratory 160 may, in some instances, generate thereports at predetermined intervals or in response to received requests(e.g., from requesting party 130, manufacturer 110, etc.), and mayprovide the generated reports to various parties and entities withinenvironment 100 (e.g., across network 150).

In some embodiments, laboratory 160 may access the centralizedrepository to identify at least one supply chain component (e.g.,manufacturer 110) associated with at least one chemical marker and/or atleast one taggant chemical marker amount identified by laboratory 160(e.g., using any of the analytical techniques outlined above) andadditionally or alternatively, obtained from any third party or otherentity within environment 100. Further, and as described below, thecentralized repository may enable laboratory 160 to determine whetherproposed chemical markers, taggant chemical marker amounts, and/ornumbers of taggant chemical marker amounts (e.g., as selected bymanufacturer 110) are capable of uniquely representing fibers and fiberproducts of manufacturer 110 that are introduced into the supply chain.

In certain embodiments, laboratory 160 may receive proposed chemicalmarkers, taggant chemical marker amounts, and/or numbers of taggantchemical marker amounts from manufacturer 110. Laboratory 160 may, forexample, compare the proposed chemical markers, taggant chemical markeramounts, and/or numbers of taggant chemical marker amounts against theestablished data records (e.g., within the centralized repository) todetermine whether these proposed chemical markers, taggant chemicalmarker amounts, and/or numbers of taggant chemical marker amounts arecapable of uniquely identifying manufacturer 110 (e.g., that theproposed chemical markers, taggant chemical marker amounts, and/ornumbers of taggant chemical marker amounts are assigned to no othersupply chain components, such as another manufacturer). If the proposedchemical markers, taggant chemical marker amounts, and/or numbers oftaggant chemical marker amounts could uniquely represent manufacturer110, laboratory 160 may assign the proposed chemical markers, taggantchemical marker amounts, and/or numbers of taggant chemical markeramounts to manufacturer 110, update the data records to reflect theassignment, and provide confirmation of the assignment to manufacturer110 (e.g., between computing systems of laboratory 160 and manufacturer110 across network 150).

Alternatively, if laboratory 160 previously assigned the proposedchemical markers, taggant chemical marker amounts, and/or numbers oftaggant chemical marker amounts to another manufacturer (or the proposedchemical markers, taggant chemical marker amounts, and/or numbers oftaggant chemical marker amounts are inappropriate to representmanufacturer 110), laboratory 160 may assign alternate chemical markers,taggant chemical marker amounts, and/or numbers of taggant chemicalmarker amounts to manufacturer 110, update the data records to reflectthe alternate assignment, and provide confirmation of the alternateassignment to manufacturer 110. In other aspects, laboratory 160 couldprovide, to manufacturer 110, an indication of the assignment of theproposed chemical markers, taggant chemical marker amounts, and/ornumbers of taggant chemical marker amounts to another manufacturer, andrequest that manufacturer 110 propose additional chemical markers,taggant chemical marker amounts, and/or numbers of taggant chemicalmarker amounts for assignment by laboratory 160, as described above.

In certain aspects, upon confirmation of the assignment, manufacturer110 may obtain and/or produce identification fibers that include theassigned chemical markers. For example, the assigned chemical markersmay be present within the obtained or produced identification fibers incorresponding chemical marker amounts (e.g., by weight of theidentification fibers), at least a portion of which correspond to theassigned taggant chemical marker amounts.

In other aspects, however, manufacturer 110 may further correlate theassigned chemical markers, taggant chemical marker amounts, and/ornumbers of taggant chemical marker amounts to one or more upstreamcomponents of the supply chain (e.g., a manufacture site, amanufacturing line, a production run, a production date, a bale) and/orvarious downstream components of the supply chain (e.g., a warehouse, acustomer, a ship-to location, etc.). For example, manufacturer 110 mayfurther specify assigned one or more of chemical markers, taggantchemical marker amounts, and/or numbers of taggant chemical markeramounts to uniquely represent a particular customer within the supplychain (e.g., customer 120).

The disclosed embodiments are, however, not limited to techniques thatenable manufacturer 110 to correlate customer 120 to assigned chemicalmarkers, taggant chemical marker amounts, and/or numbers of taggantchemical marker amounts. In further embodiments, manufacturer 110 mayspecify any additional or alternate taggant information to representother upstream or downstream supply components (or combinations thereof)in conjunction with the assigned chemical markers, taggant chemicalmarker amounts, and/or numbers of taggant chemical marker amounts.

In some aspects, while laboratory 160, or another entity, may maintaininformation linking manufacturer 110 to assigned chemical markers,taggant chemical marker amounts, and/or numbers of taggant chemicalmarker amounts, manufacturer 110 may hold confidential additionaltaggant information (e.g., non-assigned chemical markers, non-assignedtaggant chemical marker amounts, etc.) that links identification fibers,and thus fiber products produced by manufacturer 110, to other upstreamand downstream components of the supply chain. The confidentiality ofthe additional taggant information may, in certain instances, enablemanufacturer 110 to prevent laboratory 160 from identifying customers(e.g., customer 120), ship-to locations, warehouses, and other internalsupply chain components (e.g., manufacture site or line, and productionrun or date) associated with manufacturer 110.

The embodiments described above identify particular combinations oftaggant information that correlate to a specific component of a supplychain and, when present in identification fibers of a sample, enable alaboratory, a manufacturer, or other entities to identify the specificsupply chain component associated with the sample. One of ordinary skillin the art would, however, understand that the disclosed embodiments arenot limited to the particular combinations or taggant informationoutlined above, and in further embodiments, specific supply chaincomponents may be correlated with any additional or alternate physical,chemical, and/or optical characteristic exhibited by the identificationfibers. Moreover, while not depicted in FIGS. 1A and 1B, one of skill inthe art would understand that entities associated with environment 100(shown and not shown) may employ one or more warehouses to store rawmaterials, intermediate products, final stage products, etc. inconducting operations consistent with disclosed embodiments.

FIG. 2 illustrates a non-limiting example of a computing system 200 usedby one or more entities consistent with disclosed embodiments.Variations of exemplary system 200 may be used by manufacturer 110(e.g., as manufacturer system 112), customer 120, requesting party 130,and/or laboratory 160 (e.g., as laboratory system 162). In oneembodiment, system 200 may comprise one or more processors 221, one ormore input/output (I/O) devices 222, and one or more memories 223. Insome embodiments, system 200 may take the form of a server, mainframecomputer, or any combination of these components. In some embodiments,system 200 may take the form of a mobile computing device such as asmartphone, tablet, laptop computer, or any combination of thesecomponents. Alternatively, system 200 may be configured as a particularapparatus, embedded system, dedicated circuit, and the like based on thestorage, execution, and/or implementation of the software instructionsthat perform one or more operations consistent with the disclosedembodiments.

Processor 221 may include one or more known processing devices, such asmobile device microprocessors or any various other processors. Thedisclosed embodiments are not limited to any type of processor(s)configured in system 200.

Memory 223 may include one or more storage devices configured to storeinstructions used by processor 224 to perform functions related to thedisclosed embodiments. For example, memory 223 may be configured withone or more software instructions, such as program(s) 224 that mayperform one or more operations consistent with disclosed embodimentswhen executed by processor 221. The disclosed embodiments are notlimited to separate programs or computers configured to performdedicated tasks. For example, memory 223 may include a single program224 that performs the functions of system 200, or program 224 maycomprise multiple programs. Memory 223 may also store data 225 that isused by one or more programs 212, such as correlation data mappingdistinct features to one or more components of the supply chaininformation.

I/O devices 222 may be one or more devices configured to allow data tobe received and/or transmitted by system 200. I/O devices 222 mayinclude one or more digital and/or analog devices that allow componentsof environment 100 to communicate with other machines and devices, suchas other components of environment 100. For example, I/O devices 222 mayinclude a screen for displaying messages, distinct feature information,supply chain information, or providing other information to the user,such as an employee of manufacturer 110, customer 120, requesting party130, and/or laboratory 160. I/O devices 222 may also include one or moredigital and/or analog devices that allow a user to interact with system200 such as a touch-sensitive area, keyboard, buttons, or microphones.I/O devices 222 may also include other components known in the art forinteracting with a user.

The components of system 200 may be implemented in hardware, software,or a combination of both hardware and software, as will be apparent tothose skilled in the art. For example, although one or more componentsof system 200 may be implemented as computer processing instructions,all or a portion of the functionality of system 200 may be implementedinstead in dedicated electronics hardware.

System 200 may also be communicatively connected to one or moredatabase(s) 227. System 200 may be communicatively connected todatabase(s) 227 through network 150. Database 227 may include one ormore memory devices that store information and are accessed and/ormanaged through system 200. By way of example, database(s) 227 mayinclude Oracle™ databases, Sybase™ databases, or other relationaldatabases or non-relational databases, such as Hadoop sequence files,HBase, or Cassandra.

Systems and methods of disclosed embodiments, however, are not limitedto separate databases. In one aspect, system 200 may include database227. Alternatively, database 227 may be located remotely from the system200. Database 227 may include computing components (e.g., databasemanagement system, database server, etc.) configured to receive andprocess requests for data stored in memory devices of database(s) 227and to provide data from database 227.

Although the above description has designated laboratory 160 as theentity assigning various taggant information, in other aspects,manufacturer 110, customer 120, requesting party 130 or a third-partyentity not shown may be the one assigning taggants for identificationfibers. Furthermore, as seen from FIGS. 1A and 1B, although thedescription has focused on cellulose acetate tow and the black marketassociated with cigarette filters, the embodiments clearly apply tofibers of any material and any article subject to illicit trade.

FIG. 3 illustrates a non-limiting example of a process for embeddingsupply chain information into fibers, as seen and described above withrespect to disclosed embodiments.

FIG. 4 illustrates a non-limiting example of a process for generatingcorrelation data, as seen and described above with respect to disclosedembodiments. For example, as described in FIG. 4, manufacturer 110 (andadditionally or alternatively, laboratory 160) may generate a firststructured list of the supply chain components having one or morecorresponding attributes, and may generate a second structured list ofchemical markers available for inclusion within identification fibers.In some aspects, manufacturer 110 may identify one or more taggantchemical marker amounts that are available and appropriate for inclusionwithin the identification fibers (e.g., as selected from an assignednumber of taggant chemical marker amounts for the available chemicalmarkers), and may generate a third structured list of combinations ofthe chemical markers included in the first structured list and the oneor more taggant chemical marker amounts. Manufacturer 110 may also map(i) elements of the first structured list to elements of the secondstructured list and (ii) elements of the first structured list toelements of the third structured list. Manufacturer 110 may, inadditional aspects, store correlation data (e.g., in database 227)reflecting the mapping of the elements of the first and secondstructured lists and the mapping of the elements of the first and thirdstructured lists.

FIG. 5 illustrates a non-limiting example of a process for generatingcorrelation data, as seen and described above with respect to disclosedembodiments. For example, as described in FIG. 5, manufacturer 110 (andadditionally or alternatively, laboratory 160) may generate a firststructured list of the supply chain components having one or morecorresponding attributes, and may generate a second structured list ofchemical markers available for inclusion within identification fibers.In some aspects, manufacturer 110 may generate a third structured listidentifying numbers of taggant chemical marker amounts (e.g., of theavailable chemical markers) that are capable of representing the supplychain components included within the first structured list. Manufacturer110 may also map (i) elements of the first structured list to elementsof the second structured list and (ii) elements of the first structuredlist to elements of the third structured list. Manufacturer 110 may, inadditional aspects, store correlation data (e.g., in database 227)reflecting the mapping of the elements of the first and secondstructured lists and the mapping of the elements of the first and thirdstructured lists.

FIG. 6 illustrates a non-limiting example of a process for producingidentification fibers, as seen and described above with respect todisclosed embodiments.

FIG. 7 illustrates a non-limiting example of a process for identifyingat least one supply chain component associated with a fiber sample, asseen and described above with respect to disclosed embodiments.

FIG. 8 illustrates a non-limiting example of a process for identifyingchemical markers from identification fibers, as seen and described abovewith respect to disclosed embodiments.

FIG. 9 illustrates a non-limiting example of a process for assigning, tosupply chain components, combinations of distinct features and taggantfiber counts that uniquely represent the supply chain components, asseen and described above with respect to disclosed embodiments.

Listed below are non-limiting embodiments A1-A24.

A1. Fibers comprising identification fibers, wherein the identificationfibers comprise 1 to 100, 1 to 50, 1 to 20, or 1 to 10 chemical markers,wherein an amount of each of the chemical markers, based on a weight ofthe fibers, is defined as a chemical marker amount, wherein at least oneof the chemical marker amounts corresponds to a taggant chemical markeramount, and wherein (i) the chemical markers and (ii) the at least onetaggant chemical marker amounts are representative of at least onesupply chain component of the fibers.

A2. The fibers of embodiment A1, further comprising standard fibers.

A3. The fibers of any of embodiments A1 or A2, wherein one or more ofthe chemical markers are selected from the group consisting of one ormore taggant non-volatile organic compounds, one or more taggantphotoluminescent materials, one or more taggant polymeric additives, oneor more taggant carbohydrates, one or more taggant metal oxides, one ormore taggant inorganic salts, one or more taggant optical isomers, andone or more taggant isotopically labeled molecules and wherein a numberof the taggant chemical marker amounts for each of the chemical makersranges from 1 to 20.

A4. The fibers of embodiment A3, wherein a number of the taggantnon-volatile organic compounds ranges from 1 to 50, 1 to 20, or 1 to 10.

A5. The fibers of embodiment A4, wherein the taggant non-volatileorganic compounds comprise fatty acids and wherein the fatty acidscomprise lauric acid, palmitic acid, or stearic acid.

A6. The fibers of any of embodiments A3-A5, wherein a number of thetaggant photoluminescent materials ranges from 1 to 10 or 1 to 5,wherein the taggant photoluminescent materials comprise phosphorescentquantum dots, and wherein the phosphorescent quantum dots comprise Cd/Seligand stabilized fluorescent nano-crystals.

A7. The fibers of any of embodiments A3-A6, wherein a number of thetaggant polymeric additives ranges from 1 to 20 or 1 to 10 or 1 to 5,wherein the taggant polymeric additives comprise polystyrene, andwherein an average molecular weight of the polystyrene ranges from 500to 20,000,000, or wherein an average molecular weight of the polystyreneranges from 500 to 500,000, or wherein an average molecular weight ofthe polystyrene ranges from 1000 to 100,000.

A8. The fibers of any of embodiments A3-A7, wherein the chemical markerscomprise the taggant metal oxides or the taggant inorganic salts,wherein a number of the taggant metal oxides ranges from 1 to 20 or 1 to10, wherein the taggant metal oxides comprise titanium dioxide,zirconium oxides, zinc oxides, aluminum oxides, manganese oxides,magnesium oxides, calcium oxides, tin oxides, vanadium oxides, nickeloxides or iron oxides, or wherein a number of the taggant inorganicsalts ranges from 1 to 20 or 1 to 10, and wherein the taggant inorganicsalts comprise salts of cesium, indium, or samarium.

A9. The fibers of any of embodiments A1-A8, wherein an amount of each ofthe chemical markers ranges from 1 ppb to 10,000 ppm, 100 ppb to 10,000ppm, or 1 ppm to 2,000 ppm, based on the weight of the fibers.

A10. The fibers of any of embodiments A2-A9, wherein the fibers compriseacrylic, modacrylic, aramid, nylon, polyester, polypropylene, rayon,polyacrylonitrile, polyethylene, PTFE, or cellulose acetate or whereinthe identification fibers comprise acrylic, modacrylic, aramid, nylon,polyester, polypropylene, rayon, polyacrylonitrile, polyethylene, PTFE,or cellulose acetate, and the standard fibers comprise celluloseacetate.

A11. The fibers of any of embodiments A1-A10, wherein the at least onesupply chain component comprises a manufacturer of the fibers, amanufacture site of the fibers, a manufacturing line of the fibers, aproduction run of the fibers, a production date of the fibers, a packageof the fibers, a warehouse of the fibers, a customer of the fibers, aship-to location of the fibers, a manufacturer of a fiber bandcomprising the fibers, a manufacturing site of the fiber band, amanufacturing line of the fiber band, a production run of the fiberband, a production date of the fiber band, a package of the fiber band,a warehouse of the fiber band, a customer of the fiber band, a ship-tolocation of the fiber band, a manufacturer of an article comprising thefibers, a manufacture site of the article, a manufacturing line of thearticle, a production run of the article, a production date of thearticle, a package of the article, a warehouse of the article, acustomer of the article, or a ship-to location of the article.

A12. The fibers of any of embodiments A2-A11, wherein the at least onesupply chain component comprises a manufacturer of the standard fibers,a manufacture site of the standard fibers, a manufacturing line of thestandard fibers, a production run of the standard fibers, a productiondate of the standard fibers, a package of the standard fibers, awarehouse of the standard fibers, a customer of the standard fibers, aship-to location of the standard fibers, a manufacturer of a fiber bandcomprising the fibers, a manufacturing site of the fiber band, amanufacturing line of the fiber band, a production run of the fiberband, a production date of the fiber band, a package of the fiber band,a warehouse of the fiber band, a customer of the fiber band, a ship-tolocation of the fiber band, a manufacturer of an article comprising thefibers, a manufacture site of the article, a manufacturing line of thearticle, a production run of the article, a production date of thearticle, a package of the article, a warehouse of the article, acustomer of the article, or a ship-to location of the article.

A13. The fibers of embodiment A12, wherein the at least one supply chaincomponent comprises the manufacturer of the standard fibers and thecustomer of the standard fibers.

A14. A fiber band comprising the fibers of any of embodiments A1-A13,wherein the fibers comprise cellulose acetate, wherein the fiber band isan acetate tow band, and wherein (i) the chemical markers and (ii) theat least one taggant chemical marker amounts are representative of atleast one supply chain component of the acetate tow band.

A15. The fiber band of embodiment A14, wherein the at least one supplychain component comprises the manufacturer of the acetate tow band andthe customer of the acetate tow band or wherein the at least one supplychain component comprises the manufacturer of the acetate tow band andthe ship-to location of the acetate tow band.

A16. A method for making the fiber band of any of embodiments A14 or A15wherein the method comprises (a) obtaining the identification fibers;(b) producing the standard fibers on a first fiber production process;and (c) combining the standard fibers with the identification fibersinto the acetate tow band, wherein (i) the chemical markers and (ii) theleast one taggant chemical marker amounts are representative of at leastone supply chain component of the acetate tow band.

A17. The method of embodiment A16, wherein the obtaining of theidentification fibers comprises at least one of (i) producing a portionof the identification fibers on the first fiber production process, (ii)producing a portion of the identification fibers on a second fiberproduction process, or (iii) receiving a portion of the identificationfibers from a third party.

A18. The method of any of embodiments A16 or A17, wherein one or more ofthe chemical markers is added to a spinning solution upstream of thefirst fiber production process, at a spinning cabinet contained withinthe first fiber production process, or at an individual spinneretcontained within the spinning cabinet.

A19. The method of any of embodiments A16-A18, wherein one or more ofthe chemical markers are applied to a portion of the identificationfibers at any point before the combining of the standard fibers andidentification fibers into the acetate tow band.

A20. The method of any of embodiments A16-A19. wherein the methodcomprises: (a) co-producing the identification fibers and the standardfibers; and (b) combining the identification fibers and the standardfibers into the acetate tow band.

A21. A method for characterizing a fiber sample wherein the fiber samplecomprises the fibers of any of embodiments A1-A13 or the fiber band ofany of embodiments A14 or A15, wherein the method comprises: (a)dissolving the fiber sample in a solvent to produce a sample solutionand/or insolubles; (b) analyzing the sample solution and/or theinsoluble to identify the chemical markers and each of the chemicalmarker amounts.

A22. The method of embodiment A21, further comprising addingN,O-bis(trimethylsilyl)trifluoroacetamide to the sample solution.

A23. The method of any of embodiments A21 or A22, wherein the solventcomprises acetone, tetrahydrofuran, dichloromethane, methanol,chloroform, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methylacetate, ethyl acetate, nitric acid or pyridine; or wherein the solventcomprises acetone, tetrahydrofuran, nitric acid, or pyridine.

A24. The method of any of embodiments A21-A23, wherein the analyzingcomprises a use of mass spectrometry, spectroscopy, nuclear magneticresonance, x-ray diffraction, chromatography, gas chromatography coupledto flame ionization detection, size exclusion chromatography followed byUV-vis spectroscopy, fluorescence spectroscopy, inductively coupledplasma (ICP) followed by mass spectrometry, or ICP followed by opticalemission spectrometry.

A25. The method of any of embodiments A21-A24, further comprising (a)correlating one or more of the chemical markers and/or taggant chemicalmarker amounts to a database, wherein the database comprisesmanufacturer specific taggants; and (b) determining the at least onesupply chain component of the fiber sample.

EXAMPLES

Eastman™ Cellulose Acetate for fibers (CA-394-60S) was obtained fromEastman Chemical Company. Acetone (99.7%) was purchased from J. T.Baker. Cesium(I) nitrate (99.9%), indium(III) chloride tetrahytdrate(97%) & samarium(III) chloride hexahydrate (99%) lauric acid (99%),palmitic acid (98%) and stearic acid (97%) methyl laurate (99%), methylpalmitate (99%), methyl stearate (99%) was purchased from Sigma Aldrich.Low polydispersity polystyrene standards with molecular weights of70,600, 28,500 and 2,400 were purchased from Polymer Laboratories LTD.All materials were used as received. A set of alkyl ligated, Cd/Se ZnSalloyed quantum dots, with emission wavelengths of 490λ, 535λ, 575λ,630λ & 665λ were purchased from Sigma Aldrich and sourced fromCytodiagnostics Inc. Each 1 mL sample was received as a 1 mg/mL solutionand kept under refrigeration until use.

In all of the tables below, spike concentration in ppm is calculatedbased upon the measured amounts of chemical marker added to the measuredamount of cellulose acetate. Recovered concentration in ppm is basedupon analytical measurement.

Analytical Methods

Inductively Coupled Plasma Mass Spectrometry (ICP-MS)—Metalconcentrations were measured using an Elan 6100 Inductively CoupledPlasma Mass Spectrometer ICP-MS (Perkin Elmer Corp, Norwalk, Conn.).Sample digestion was performed using an UltraWAVE Single ReactionChamber (SRC) (Milestone, Shelton Conn.) or bulk digestions in HNO₃ on ahotplate. Samples were prepared by weighing ˜0.25 g into a cleanedquartz tube, 4 ml HNO₃ was then added and the tube was capped anddigested using a preprogrammed set of conditions. Bulk digestion wascarried out on a 1 gram film sample, transferred into a 150 mL quartzbeaker to which 10 mL of HNO₃ acid was added and heated on a hot platefor 2 hrs at 200° C. or until the sample had completely digested. Oncedigested the sample was quantitatively transferred to a 100 mLvolumetric flask and diluted with HNO₃. Samples were then quantitativelytransferred to a 25 mL volumetric flask using Millipore water. ARubidium internal standard was added and the samples were analyzed byICP-MS. The ICP-MS was calibrated at 5 part per billion using matrixmatched standards prepared from certified calibration standardspurchased from High Purity Standards (Charleston, S.C.). The calibratedmasses were samarium—151.92, cesium—132.905 and indium—114.904.

Gas Chromatography-Flame Ionization Detection (GC-FID)—The concentrationof taggant fatty acid in cellulose acetate (CA) was determined via aninternal standard-based, gas chromatography method. A Shimadzu 2010 gaschromatograph with CombiPAL autosampler and flame ionization detector(FID) was utilized; a DB-5 (30 m×0.32 mm×0.25 μm) capillary column wasused. Samples were prepared by weighing ˜0.05 g of tagged CA into a 2 mLglass GC vial; 500 μL of internal standard solution (0.1% (w/v) dodecanein pyridine) was then added to the vial using an eVol digital pipetteequipped with a 500 μL tip. Samples were then heated at 80° C. for tenminutes. After heating, 1.00 mL ofN,O-Bis(trimethylsilyl)trifluoroacetamide (BSTFA) was added toderivatize the fatty acid taggant. Samples were heated at 80° C. forfive minutes, vortexed, then heated at 80° C. for 25 minutes. Thesamples were subsequently centrifuged at 5,000 rpm for 10 minutes (VWRClinical 200); the supernatant was subsequently transferred to a secondGC vial containing a 300 μL glass insert.

Gel Permeation Chromatography with UV Detection—An Agilent series 1100liquid chromatographic instrument was used. The instrument consists of adegasser, an isocratic pump, an auto-sampler, a column oven, arefractive index detector and a UV/VIS detector. The column setconsisted of Agilent PLgel 5 micron guard, Mixed-C and Oligopore columnsin series. The solvent used to dissolve the samples and as the eluentfor the system was stabilized tetrahydrofuran. The flow rate for thesystem was set at 1.0 ml/min. The auto-sampler used an injection volumeof 50 μl. The column oven was set at 30° C. The refractive indexdetector was set at 30° C. The UV/VIS detector was set at 260 nm fordetection purposes. The instrument was calibrated using a set of 14mono-disperse polystyrene standards ranging from 3,220,000 to 580molecular weight and a 162 molecular weight phenyl hexane.

Fluorescence Spectroscopy—All samples were stored in a dark refrigeratoruntil the spectra were acquired. The fluorescence spectra were collectedusing a Horiba Fluorolog®-3-22 Spectrofluorometer. Samples were placedin quartz fluorescence cells and excited at 295 nm with the emissionrecorded from 200 nm to 800 nm. All slits were set to 1 nm and a 0.1 sintegration time was used. All data is reported normalized by the lampintensity at the time of measurement in CPS/microamps.

Example 1

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of cesium (I) nitrate (0.68mg/mL in cesium), prepared in a 9:1 acetone/water solution, and wasadded to the mixture to give a dope that was 68 ppm in cesium based ontotal solids. The vial was then placed on a continuous roller for aminimum of 16 hours or until a homogenous dope was formed. The dope wasthen poured into labeled culture dish bottoms (100 mm×20 mm) set in atransparent container with a cover. The solvent was allowed to slowlyevaporate under cover for 5 hrs. The cover was then removed and thesamples allowed to dry further under the draft of the fume hood for 1hr. The samples were then removed from the dishes and submitted forICP-MS analysis. The calculated spiked concentration of cesium, themeasured concentration of cesium and the Recovery calculated as thepercent measured divided by spiked are given in Table 1. All metalconcentrations are based on metal alone.

Examples 2-5

Example 1 was repeated to prepare four additional films, by linearlyincreasing the concentration by a factor of two in each film. Theresults are summarized in Table 1.

Example 6

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of indium(III) chloridetetrahydrate (0.39 mg/mL in indium), prepared in a 9:1 acetone/watersolution, and was added to the mixture to give a dope that was 39 ppm inIndium based on total solids. The vial was then placed on a continuousroller for a minimum of 16 hours or until a homogenous dope was formed.The dope was then poured into labeled culture dish bottoms (100 mm×20mm) set in a transparent container with a cover. The solvent was allowedto slowly evaporate under cover for 5 hrs. The cover was then removedand the samples allowed to further dry under the draft of the fume hoodfor 1 hr. The samples were then removed from the dishes and submittedfor ICP-MS analysis. The calculated spiked concentration of indium, themeasured concentration of indium, and the % Recovery calculated as thepercent measured divided by spiked are given in Table 1.

Examples 7-10

Example 6 was repeated to prepare four additional films, by linearlyincreasing the concentration by a factor of two in each film. Theresults are summarized in Table 1 including the spiked and recoveredamounts and percent recovery.

Example 11

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of samarium(III) chloridehexahydrate (0.41 mg/mL in samarium), prepared in a 9:1 acetone/watersolution, and was added to the mixture to give a dope that was 41 ppm insamarium based on total solids. The vial was then placed on a continuousroller for a minimum of 16 hours or until a homogenous dope was formed.The dope was then poured into labeled culture dish bottoms (100 mm×20mm) set in a transparent container with a cover. The solvent was allowedto slowly evaporate under cover for 5 hrs. The cover was then removedand the samples allowed to further dry under the draft of the fume hoodfor 1 hr. The samples were then removed from the dishes and submittedfor ICP-MS analysis. The calculated spiked concentration of samarium,the measured concentration of samarium and the % Recovery calculated asthe percent measured divided by spiked are given in Table 1.

Examples 12-15

Example 11 was repeated to prepare four additional films, by linearlyincreasing the concentration by a factor of two in each film. Theresults are summarized in Table 1.

TABLE 1 Examples of Metal Recovered Cellulose Acetate Films SpikedRecovered Example Metal Conc. (ppm) Conc. (ppm) % Recovery 1 Cesium 6854 79 2 Cesium 136 109 80 3 Cesium 204 169 83 4 Cesium 272 265 97 5Cesium 340 285 84 6 Indium 39 30 77 7 Indium 78 65 83 8 Indium 117 96 829 Indium 156 129 83 10 Indium 195 166 85 11 Samarium 41 35 85 12Samarium 82 63 77 13 Samarium 123 96 78 14 Samarium 164 140 85 15Samarium 205 175 85

Example 16

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 300 μL of a 1.0 mg/mL stock solution of samarium(III) chloridehexahydrate (0.41 mg/mL in samarium) stock solution, 100 μL of a 1.0mg/mL stock solution of cesium(I) nitrate (0.68 mg/mL in cesium) stocksolution and 200 μL of a 1.0 mg/mL stock solution of indium(III)chloride tetrahydrate (0.39 mg/mL in Indium) was added to the mixture togive a dope that was 123 ppm in samarium, 68 ppm in cesium, and 78 ppmin indium, respectively, based on polymer solids. The vial was thenplaced on a continuous roller for a minimum of 16 hours or until ahomogenous dope was formed. The dope was then poured into labeledculture dish bottoms (100 mm×20 mm) set in a transparent container witha cover. The solvent was allowed to slowly evaporate under cover for 5hrs. The cover was then removed and the samples allowed to further dryunder the draft of the fume hood for 1 hr. The samples were then removedfrom the dishes and submitted for ICP-MS analysis. The calculated spikedconcentration of samarium, cesium and indium, the measured concentrationof samarium, cesium and indium, and the % Recovery calculated as thepercent measured divided by spiked are given in Table 2.

Examples 17-19

Example 16 was repeated to prepare three additional films with varyingamounts of each metal. The results are summarized in Table 2.

TABLE 2 Examples of Cellulose Acetate Films Containing Multiple MetalsSpiked Conc.(ppm) Recovered Conc.(ppm) Example Samarium Cesium IndiumSamarium Cesium Indium 16 123 68 78 107 56 66 17 82 272 117 66 232 10318 41 204 195 33 167 168 19 205 136 156 178 113 140

Examples 16-19 demonstrate that metal salts can be used as chemicaltaggants and that different amounts of the metal salts can be detectedand use in a code for tracking and tracing material through the supplychain.

Example 20

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of lauric acid, prepared inacetone, was added to the mixture to give a dope that was 100 ppm inlauric acid based on total solids. GC analysis of this stock solutionreported the true concentration to be 0.908 g/mL. The vial was thenplaced on a continuous roller for a minimum of 16 hours or until ahomogenous dope was formed. The dope was then poured into labeledculture dish bottoms (100 mm×20 mm) set in a transparent container witha cover. The solvent was allowed to slowly evaporate under cover for 5hrs. The cover was then removed and the samples allowed to dry furtherunder the draft of the fume hood for 1 hr. The samples were then removedfrom the dishes and submitted for GC-FID analysis. All samples wereprepared in duplicate. The levels of chemical taggant are reported asthe average value with error bars corresponding to (+/−) one standarddeviation.

Examples 21-24

Example 20 was repeated to prepare four additional films, by linearlyincreasing the concentration in increments of 100 ppm in each film. Theresults are summarized in Table 3.

Example 25

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of palmitic acid, preparedin acetone, was added to the mixture to give a dope that was 100 ppm inpalmitic acid based on total solids. GC analysis of this stock solutionreported the true concentration to be 1.10 g/mL. The vial was thenplaced on a continuous roller for a minimum of 16 hours or until ahomogenous dope was formed. The dope was then poured into labeledculture dish bottoms (100 mm×20 mm) set in a transparent container witha cover. The solvent was allowed to slowly evaporate under cover for 5hrs. The cover was then removed and the samples allowed to dry furtherunder the draft of the fume hood for 1 hr. The samples were then removedfrom the dishes and submitted for GC-FID analysis. All samples wereprepared in duplicate and the results are given in Table 3.

Examples 26-29

Example 25 was repeated to prepare four additional films, by linearlyincreasing the concentration in increments of 100 ppm in each film. Theresults are summarized in Table 3.

Example 30

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of stearic acid, preparedin acetone, was added to the mixture to give a dope that was 100 ppm instearic acid based on total solids. GC analysis of this stock solutionreported the true concentration to be 0.888 g/mL. The vial was thenplaced on a continuous roller for a minimum of 16 hours or until ahomogenous dope was formed. The dope was then poured into labeledculture dish bottoms (100 mm×20 mm) set in a transparent container witha cover. The solvent was allowed to slowly evaporate under cover for 5hrs. The cover was then removed and the samples allowed to dry furtherunder the draft of the fume hood for 1 hr. The samples were then removedfrom the dishes and submitted for GC-FID analysis. All samples wereprepared in duplicate and the results are given in Table 3.

Examples 31-34

Example 30 was repeated to prepare four additional films, by linearlyincreasing the concentration in increments of 100 ppm in each film. Theresults are summarized in Table 3 including the spiked and recoveredconcentration of stearic acid and percent recovery.

TABLE 3 Examples of Fatty Acid Spiked Cellulose Acetate Films DuplicateSamples Spiked Recovered Recovered Fatty Conc. Conc. Conc. Average %Example Acid (ppm) (ppm) (ppm) Recovery 20 Lauric 91 71 91 81 21 Lauric182 173 172 86 22 Lauric 272 275 263 90 23 Lauric 363 361 376 92 24Lauric 454 450 464 91 25 Palmitic 110 111 101 106 26 Palmitic 220 212213 106 27 Palmitic 330 337 323 110 28 Palmitic 440 462 424 110 29Palmitic 550 630 536 116 30 Stearic 89 91 100 96 31 Stearic 178 180 233103 32 Stearic 266 270 274 91 33 Stearic 355 365 371 92 34 Stearic 444449 435 88

Examples 35-38

The procedure of Example 20 was repeated to prepare four additionalfilms, comprising varying concentrations of lauric acid, palmitic acid,and stearic acid. The results are summarized in Table 4 including thespiked and recovered concentrations of each fatty acid and percentrecovery.

TABLE 4 Examples of Cellulose Acetate Films Containing Multiple FattyAcids Duplicate Samples Spiked Conc.(ppm) Recovered Conc.(ppm) RecoveredConc.(ppm) Average % Recovery Example Lauric Palmitic Stearic LauricPalmitic Stearic Lauric Palmitic Stearic Lauric Palmitic Stearic 35 182330 444 162 294 385 171 302 413 92 90 90 36 363 330 178 327 286 164 326305 163 90 90 92 37 272 550 89 251 513 90 253 535 91 93 95 102 38 454220 355 425 212 334 478 229 374 99 100 100

Example 39

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of methyl laurate, preparedin acetone, was added to the mixture to give a dope that was 100 ppm inmethyl laurate based on total solids. GC analysis of this stock solutionreported the true concentration to be 1.22 g/mL. The vial was thenplaced on a continuous roller for a minimum of 16 hours or until ahomogenous dope was formed. The dope was then poured into labeledculture dish bottoms (100 mm×20 mm) set in a transparent container witha cover. The solvent was allowed to slowly evaporate under cover for 5hrs. The cover was then removed and the samples allowed to dry furtherunder the draft of the fume hood for 1 hr. The samples were then removedfrom the dishes and submitted for GC-FID analysis. All samples wereprepared in duplicate and the results are summarized in Table 5.

Examples 40-43

Example 39 was repeated to prepare four additional films, by linearlyincreasing the concentration in increments of 100 ppm in each film. Theresults are summarized in Table 5.

Example 44

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of methyl palmitate,prepared in acetone, was added to the mixture to give a dope that was100 ppm in methyl palmitate based on total solids. GC analysis of thisstock solution reported the true concentration to be 1.37 g/mL. The vialwas then placed on a continuous roller for a minimum of 16 hours oruntil a homogenous dope was formed. The dope was then poured intolabeled culture dish bottoms (100 mm×20 mm) set in a transparentcontainer with a cover. The solvent was allowed to slowly evaporateunder cover for 5 hrs. The cover was then removed and the samplesallowed to dry further under the draft of the fume hood for 1 hr. Thesamples were then removed from the dishes and submitted for GC-FIDanalysis. All samples were prepared in duplicate. The results aresummarized in Table 5.

Examples 45-48

Example 44 was repeated to prepare four additional films, by linearlyincreasing the concentration in increments of 100 ppm in each film. Theresults are summarized in Table 5.

TABLE 5 Examples of Fatty Acid Methyl Ester Recovered Film SamplesDuplicate Samples Spiked Recovered Recovered Sam- Conc. Conc. Conc.Average % ple FAME (ppm) (ppm) (ppm) Recovery 39 Methyl Laurate 122 9593 77 40 Methyl Laurate 244 173 185 73 41 Methyl Laurate 366 293 277 7742 Methyl Laurate 488 401 390 81 43 Methyl Laurate 610 477 489 79 44Methyl Palmitate 133 108 110 81 45 Methyl Palmitate 266 208 232 82 46Methyl Palmitate 399 334 354 86 47 Methyl Palmitate 532 452 425 82 48Methyl Palmitate 665 553 575 84

The fatty acid methyl ester average percent recovery was lower than whatwas seen in the fatty acids. As only a part of each film was digestedand tested, dope samples were made and tested directly to rule outvariability in concentration throughout the film.

Example 49

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of methyl palmitate,prepared in acetone, was added to the mixture to give a dope that was100 ppm in methyl palmitate based on total solids. GC analysis of thisstock solution reported the true concentration to be 1.33 g/mL. The vialwas then placed on a continuous roller for a minimum of 16 hours oruntil a homogenous dope was formed. The samples were then submitted forGC-FID analysis. All samples were prepared in duplicate and the resultsare summarized in Table 6.

Examples 50-53

Example 49 was repeated to prepare four additional dopes, by linearlyincreasing the concentration in increments of 100 ppm in each dope. Theresults are summarized in Table 6.

Example 54

A 20 mL scintillation vial was charged with cellulose acetate (1.00 g)followed by HPLC grade acetone (11.38 mL) to give a mixture 10% (w/w) insolids. 100 μL of a 1.0 mg/mL stock solution of methyl stearate,prepared in acetone, was added to the mixture to give a dope that was100 ppm in methyl stearate based on total solids. GC analysis of thisstock solution reported the true concentration to be 1.03 g/mL. The vialwas then placed on a continuous roller for a minimum of 16 hours oruntil a homogenous dope was formed. The samples were then submitted forGC-FID analysis. All samples were prepared in duplicate and the resultsare summarized in Table 6.

Examples 55-58

Example 54 was repeated to prepare four additional dopes, by linearlyincreasing the concentration in increments of 100 ppm in each dope. Theresults are summarized in Table 6.

TABLE 6 Examples of Fatty Acid Methyl Ester Recovered Dope SamplesDuplicate Samples Spiked Recovered Recovered Sam- Conc. Conc. Conc.Average % ple FAME (ppm) (ppm) (ppm) Recovery 49 Methyl Palmitate 10 7 768 50 Methyl Palmitate 20 17 15 82 51 Methyl Palmitate 29 31 30 105 52Methyl Palmitate 39 38 39 98 53 Methyl Palmitate 48 48 51 103 54 MethylStearate 10 12 12 121 55 Methyl Stearate 20 20 19 98 56 Methyl Stearate29 27 30 98 57 Methyl Stearate 39 40 40 102 58 Methyl Stearate 48 48 4597

Pilot scale evaluations of methyl laurate, methyl palmitate, and methylstearate were conducted in a similar manner as the fatty acid examplesdescribed below. The recovery of the fatty acid methyl esters was farbelow expectation. Without being bound by any theory, we hypothesizethat the fatty acid methyl esters were poorly compatible with the CApolymer and had a greater affinity for the evaporating acetone duringspinning, despite their relatively high boiling points and low vaporpressures. No further work on the fatty acid methyl esters as chemicalmarkers for inclusion with cellulose acetate was performed.

Pilot Scale Evaluation of Fatty Acids as Chemical Taggants

Fatty acids were used to produce a series of tagged cellulose acetatethreads on pilot plant equipment, each production run made 1,700 denierthreads. The spooled threads, containing known concentrations of eachfatty acid, were then combined in a modular fashion with celluloseacetate threads without any fatty acid, to produce an encoded celluloseacetate tow band having a denier of 34,000. The band of acetate tow wasthen formed into filter rods using industry standard equipment with theaddition of a plasticizer common to the industry.

The taggant threads were made by first preparing a cellulose acetatedope concentrate that contained 907 g of fatty acid, cellulose acetate,a pigment (Copper Phthalocyanine, CAS No. 147-14-8) to aid in trackingof the additive dope through the process and acetone, to create a dopecontaining 28.3% solids. This dope concentrate had a targetconcentration of 51819 ppm in fatty acid. This dope concentrate was thenmetered into virgin cellulose acetate dope through a controlled additivesystem and homogenized using an in-line mixing system. The mixed dopewas then fed through a spinning cabinet and treated with lubricant,familiar to those skilled in the art and the resultant thread collectedonto spools. The system was purged with virgin cellulose acetate dopebefore moving to the subsequent taggant mixture. The targetconcentration of fatty acid in the tagged thread was 4000 ppm.Approximately 15-20 spools of thread were generated during the spinningof a single taggant batch. Three sets of tagged spools were made in thisfashion that contained lauric, palmitic and stearic acids.

Examples 59-109

To ensure uniformity of the taggant concentration along the length ofthe thread, samples were removed from each spool in each set of fattyacid threads and analyzed via GC using FID detection as previousdescribed. The order of the examples does not represent the order inwhich each spool was produced. The results are summarized in Table 7including individual and global taggant averages, standard deviationsand percent relative standard deviations.

TABLE 7 Examples of Fatty Acid Recovered Cellulose Acetate Thread FattyRecovered Example Acid Conc. (ppm) 59 Lauric 4002 60 Lauric 3685 61Lauric 4249 62 Lauric 4321 63 Lauric 4216 64 Lauric 4444 65 Lauric 412066 Lauric 4076 Average 4230 67 Lauric 4344 STDEV 195 68 Lauric 4513 %RSD 4.61 69 Lauric 4366 % Recovery 105.75 70 Lauric 4399 71 Lauric 412972 Lauric 4200 73 Lauric 4277 74 Lauric 4212 75 Lauric 4356 76 Palmitic4455 77 Palmitic 4177 78 Palmitic 4464 79 Palmitic 4424 80 Palmitic 444281 Palmitic 4120 82 Palmitic 4010 83 Palmitic 4231 Average 4215 84Palmitic 4434 STDEV 236 85 Palmitic 4430 % RSD 5.60 86 Palmitic 4194 %Recovery 105.38 87 Palmitic 3700 88 Palmitic  1636* 89 Palmitic 4145 90Palmitic 4197 91 Palmitic 4256 92 Palmitic 3766 93 Stearic 4305 94Stearic 4435 95 Stearic 4267 96 Stearic 4004 97 Stearic 4102 98 Stearic3990 99 Stearic 4143 100 Stearic 4174 Average 4085 101 Stearic 4077STDEV 166 102 Stearic 4100 % RSD 4.08 103 Stearic 4223 % Recovery 102.13104 Stearic 3895 105 Stearic 3910 106 Stearic 4098 107 Stearic 3925 108Stearic 4013 109 Stearic 3777 Global 4151 Average Global STDEV 196Global % RSD 4.72 Global % 103.78 Recovery *Example 88 is believed torepresent an anomaly where system contamination from the previous fattyacid in the mixing system had occurred. This data point was excludedfrom the statistical treatment since this type of error was a result ofa correctable system contamination and not a reflection of the methodreliability.

Tagged spools, in addition to un-tagged spools, were then loaded onto adevice to allow the pilot-scale manufacture of a band of acetate tow.Through the addition or subtraction of a defined number of spools of aparticular taggant type, the final concentration and taggant makeup inthe tow band could be altered. The collected tow band was pressed into abale and subsequently used in the manufacture of the filter rods. Thefilter rods were made on AF2/KDF2 plugmaker at 400 m/min. The filter rodlength was 120 mm and circumference was 24.4 mm. Samples from themanufactured filter rods were prepared for GC analysis in the samemanner as previously described. Each of the examples below representanalysis of a single filter rod from the batch of filter rods produced,taken in no particular order. The code notation for the filter rodsamples correspond to the spike concentration (ppm), in the filter rodand based on the weight of cellulose acetate, of each fatty acid in theorder, lauric acid, palmitic acid, and stearic acid.

Examples 110-127

The spike concentration for lauric acid, palmitic acid, and stearic acidin Examples 110-127 were 1000-000-000. The results are summarized inTable 8.

TABLE 8 Examples of Fatty Acid Encoded Cellulose Acetate Filter Rods(Code 1000-000-000) Recovered Conc. (ppm) Lauric Palmitic StearicExample Acid Acid Acid 110 935 0 0 111 1042 0 0 112 956 0 0 113 926 0 0114 1127 0 0 115 952 0 0 116 1078 0 0 117 969 0 0 118 948 0 0 119 1042 00 120 1153 0 0 121 1121 0 0 122 1162 0 0 123 1140 0 0 124 1167 0 0 1251177 0 0 126 1174 0 0 127 1128 0 0 Average 1066 0 0 Std. Dev. 92 0 0Average % Recovery 107 N/A N/A

Examples 128-145

The spike concentration for lauric acid, palmitic acid, and stearic acidin Examples 128-145 were 000-1000-000. Filter rods were prepared in thesame manner as described above. The results are summarized in Table 9.

TABLE 9 Examples of Fatty Acid Encoded Cellulose Acetate Filter Rods(Code 000-1000-000) Recovered Conc. (ppm) Lauric Palmitic StearicExample Acid Acid Acid 128 0 1083 0 129 0 848 0 130 0 1112 0 131 0 10600 132 0 813 0 133 0 846 0 134 0 1042 0 135 0 1011 0 136 0 965 0 137 0903 0 138 0 1142 0 139 0 1207 0 140 0 1140 0 141 0 1333 0 142 0 1046 0143 0 1123 0 144 0 1028 0 145 0 1114 0 Average 0 1045 0 Std. Dev. 0 1300 Average % Recovery N/A 105 N/A

Examples 146-163

The spike concentration for lauric acid, palmitic acid, and stearic acidin Examples 146-163 were 000-000-1000. Filter rods were prepared in thesame manner as described above. The results are summarized in Table 10including the spiked and recovered amounts and percent recovery.

TABLE 10 Examples of Fatty Acid Encoded Cellulose Acetate Filter Rods(Code 000-000-1000) Recovered Conc. (ppm) Lauric Palmitic StearicExample Acid Acid Acid 146 0 0 966 147 0 0 921 148 0 0 942 149 0 0 1001150 0 0 911 151 0 0 965 152 0 0 965 153 0 0 988 154 0 0 923 155 0 0 1089156 0 0 1027 157 0 0 1079 158 0 0 1114 159 0 0 961 160 0 0 1002 161 0 0866 162 0 0 1080 163 0 0 959 Average 0 0 987 Std. Dev. 0 0 66 Average %Recovery N/A N/A 99

Examples 164-181

The spike concentration for lauric acid, palmitic acid, and stearic acidin Examples 164-181 were 600-800-1000. Filter rods were prepared in thesame manner as described above. The results are summarized in Table 11.

TABLE 11 Examples of Fatty Acid Encoded Cellulose Acetate Filter Rods(Code 600-800-1000) Recovered Conc. (ppm) Lauric Palmitic StearicExample Acid Acid Acid 164 593 839 1091 165 570 839 1115 166 612 8921232 167 571 896 1271 168 589 868 1253 169 688 995 1312 170 618 802 990171 563 803 1170 172 545 756 984 173 652 962 1440 174 703 1134 1519 175624 888 1325 176 612 792 1120 177 642 811 1017 178 744 1021 1294 179 7721061 1393 180 795 1052 1256 181 716 932 1183 Average 645 908 1220 Std.Dev. 73 105 147 Average % Recovery 107 113 122

Examples 182-199

The spike concentration for lauric acid, palmitic acid, and stearic acidin Examples 182-199 were 800-1000-600. Filter rods were prepared in thesame manner as described above. The results are summarized in Table 12.

TABLE 12 Examples of Fatty Acid Encoded Cellulose Acetate Filter Rods(Code 800-1000-600) Recovered Conc. (ppm) Lauric Palmitic StearicExample Acid Acid Acid 182 858 1025 668 183 859 904 594 184 878 987 590185 854 1081 702 186 773 968 680 187 745 855 604 188 811 914 612 189 8401021 698 190 791 949 640 191 950 1232 858 192 894 1314 851 193 865 1006724 194 974 1014 657 195 783 1011 672 196 897 1049 759 197 825 1029 763198 857 977 665 199 968 1122 687 Average 857 1025 690 Std. Dev. 63 10876 Average % Recovery 107 103 115

Examples 200-217

The spike concentration for lauric acid, palmitic acid, and stearic acidin Examples 200-217 were 1000-600-800. Filter rods were prepared in thesame manner as described above. The results are summarized in Table 13.

TABLE 13 Examples of Fatty Acid Encoded Cellulose Acetate Filter Rods(Code 800-1000-600) Recovered Conc. (ppm) Lauric Palmitic StearicExample Acid Acid Acid 200 897 570 887 201 862 558 840 202 894 616 988203 915 520 851 204 912 624 925 205 891 520 792 206 960 634 972 207 987695 1098 208 941 718 1098 209 1142 723 1173 210 1012 637 858 211 1084648 1059 212 1141 766 1091 213 1074 672 913 214 1051 606 882 215 1085684 1035 216 1158 556 869 217 1198 702 1005 Average 1011 636 963 Std.Dev. 105 70 107 Average % Recovery 101 106 120

A series of polyethylene glycols (PEG's) as chemical taggants incellulose acetate were evaluated using size exclusion chromatography asthe method of separation and refractive index (RI) as the method ofdetection. The PEG's ranged in molecular weight from 200 to 20,000.Initial screening showed poor solubility of PEG's greater than 2,000 insolvents suitable for analysis (tetrahydrofuran, methylene chloride andhexafluoroisopropanol). Poor resolution of the lower molecular weightPEG fragments using these same solvents. No further work on using PEG'sas a chemical taggant for acetate tow was pursued.

Polystyrenes are soluble in a broad range of solvents; including acetoneand have the advantage of an aromatic side group which allows fordetection via UV-Vis. Detection via UV-Vis simplifies analysis sincecellulose acetate has a low UV response at the selected wavelengths,which makes the cellulose acetate almost invisible. To determine thelinearity of signal intensity with increasing polystyrene concentration,calibration standards in THF were prepared for each polystyrene standardat 20, 30, 40, 50, and 100 ppm. These solutions were analyzed GPC withUV-Vis detection. Within this concentration range, signal intensityincreased in a linear fashion with an increase in concentration with R²values near unity.

Example 218

A cellulose acetate dope containing polystyrene taggant was made byadding 2.0 mL of the respective calibration standard solution to a vialfollowed by enough cellulose acetate powder to provide the desiredconcentration of polystyrene. The vial was then placed on a shakerapparatus and gently agitated for more than 16 hrs. The homogenous dopeswere then then analyzed via GPC with UV detection at 260 nm.

Examples 219-232

Example 218 was repeated to prepare additional dopes, for eachpolystyrene oligomer, by linearly increasing the concentration inincrements of 10 ppm in each dope up to 50 ppm and a terminal sample at100 ppm. The results are summarized in Table 14 including the spiked andrecovered amounts and percent recovery.

TABLE 14 Examples of Polystyrene Spiked Cellulose Acetate Dope SamplesDuplicate Samples Poly- Spiked Recovered Recovered Sam- styrene Conc.Conc. Conc. Average % ple Std. (ppm) (ppm) (ppm) Recovery 218  2k 20 1920 96 219  2k 30 28 30 96 220  2k 40 38 40 98 221  2k 50 46 49 94 222 2k 100 98 107 102 223 20K 20 21 22 109 224 20K 30 29 30 99 225 20K 4039 41 100 226 20K 50 49 52 101 227 20K 100 97 102 100 228 70k 20 20 22104 229 70k 30 29 31 101 230 70k 40 39 41 100 231 70k 50 49 51 100 23270k 100 97 103 100

Examples 233-235

The procedure of Example 218 was repeated to prepare three additionaldopes, with varying concentrations of all polystyrene standards. Theresults are summarized in Table 15.

TABLE 15 Examples of Polystyrene Oligomer Encoded Cellulose AcetateDopes Duplicate Samples Spiked Conc. (ppm) Recovered Conc. (ppm)Recovered Conc. (ppm) Average % Recovery 2,000 20,000 70,000 2,00020,000 70,000 2,000 20,000 70,000 2,000 20,000 70,000 Example MW MW MWMW MW MW MW MW MW MW MW MW 233 100 20 50 93 23 53 91 23 52 92 114 106234 20 50 100 16 49 97 17 49 98 83 98 98 235 50 100 20 42 88 20 43 88 2085 88 100

To determine the linearity of signal intensity with increasing alkylatedCd/Se nanocrystals concentration, calibration standards were preparedfor alkylated Cd/Se nanocrystals of each emission wavelength (490, 525,575, 630 & 665 nm) in a solution of 230 mg of cellulose acetate in THF.Solutions were prepared at 10 ppm, 8 ppm, 6 ppm, 4 ppm and 2 ppm suchthat each solution was 5% wt. solids starting from a 100 ppm stocksolutions of each Cd/Se nanocrystal in THF. These solutions were thenanalyzed via fluorescence spectroscopy. Within this concentration range,signal intensity increased in a linear fashion with an increase inconcentration with R² values ranging from 0.95-0.99.

Examples 236-239

A speed mixing cup is charged with 1.0 g of cellulose acetate and 14.46mL of THF. The container is sealed and placed on a continuous rollerovernight to give a homogenous dope. Using the previously prepared 100ppm stock solutions, varying concentrations of 525, 575 and 635 nm Cd/Senanocrystal were then added to the prepared dopes in a manner so thatall samples were 5% wt. in solids. The containers were then sealed andplaced in a speed mixer for 60 sec. at 3500 rpm. The finished dopes werethen transferred to quartz cuvettes for analysis via fluorescencespectroscopy. The results are summarized in Table 16 including thespiked and recovered amounts and percent recovery.

TABLE 16 Examples of Polystyrene Oligomer Encoded Cellulose AcetateDopes Recovered Recovered Conc. (ppm) Conc. (ppm) % Recovery Exam- 525575 665 525 575 665 525 575 665 ple nm nm nm nm nm nm nm nm nm 236 12 106 12 13 7 99 134 110 237 6 8 8 6 10 13 103 130 168 238 10 6 8 10 9 9 101142 115 239 8 12 10 8 15 10 96 125 99

Other embodiments will be apparent to those skilled in the art fromconsideration of the specification and practice of the embodimentsdisclosed herein. It will be understood that variations andmodifications can be effected within the spirit and scope of thedisclosed embodiments. It is further intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the disclosed embodiments being indicated by the following claims.

We claim:
 1. A method for characterizing a fiber sample wherein thefiber sample comprises fibers, wherein the fibers compriseidentification fibers, wherein the identification fibers comprise 1 to100 chemical markers, wherein an amount of each of the chemical markers,based on a weight of the fibers, is defined as a chemical marker amount,wherein at least one of the chemical marker amounts corresponds to ataggant chemical marker amount, and wherein (i) the chemical markers and(ii) the at least one taggant chemical marker amounts are representativeof at least one supply chain component of the fiber sample, and whereinthe method comprises: (a) dissolving the fiber sample in a solvent toproduce a sample solution and/or insolubles; (b) analyzing the samplesolution and/or the insoluble to identify the chemical markers and eachof the chemical marker amounts.
 2. The method of claim 1, wherein thefibers further comprise standard fibers.
 3. The method of claim 2,further comprising (a) correlating one or more of the chemical markersand the taggant chemical marker amounts to a database, wherein thedatabase comprises manufacturer specific taggants; and (b) determiningthe at least one supply chain component of the fiber sample, wherein theat least one supply chain component comprises a manufacturer of thestandard fibers, a manufacture site of the standard fibers, amanufacturing line of the standard fibers, a production run of thestandard fibers, a production date of the standard fibers, a package ofthe standard fibers, a warehouse of the standard fibers, a customer ofthe standard fibers, a ship-to location of the standard fibers, amanufacturer of a fiber band comprising the fibers, a manufacturing siteof the fiber band, a manufacturing line of the fiber band, a productionrun of the fiber band, a production date of the fiber band, a package ofthe fiber band, a warehouse of the fiber band, a customer of the fiberband, or a ship-to location of the fiber band.
 4. The method of claim 3,wherein the at last one supply chain component comprises themanufacturer of the standard fibers or the fiber band comprising thefibers.
 5. The method of claim 3, wherein the at last one supply chaincomponent comprises the manufacturer of the standard fibers or the fiberband comprising the fibers and the customer of the standard fibers orthe fiber band.
 6. The method of claim 3, wherein the at last one supplychain component comprises the manufacturer of the standard fibers or afiber band comprising the fibers and the ship-to location of thestandard fibers or the fiber band.
 7. The method of claim 3, wherein thefiber sample comprises a portion of a filter rod or a portion of acigarette filter.
 8. The method of claim 1, wherein the identificationfibers comprise 1 to 50 of the chemical markers.
 9. The method of claim1, further comprising adding N,O-bis(trimethylsilyl)trifluoroacetamideto the sample solution.
 10. The method of claim 1, wherein one or moreof the chemical markers is selected from the group consisting of one ormore taggant non-volatile organic compounds, one or more taggantphotoluminescent materials, one or more taggant polymeric additives, oneor more taggant carbohydrates, one or more taggant metal oxides, one ormore taggant inorganic salts, one or more taggant optical isomers, oneor more taggant isotopically labeled molecules, and one or more tagganttrace chemicals inherent to a manufacturer of the standard fibers, andwherein a number of the taggant chemical marker amounts for each of thechemical makers ranges from 1 to
 20. 11. The method of claim 10, whereina number of the taggant nonvolatile organic compounds ranges from 1 to20 and wherein the taggant non-volatile organic compounds compriselauric acid, palmitic acid, or stearic acid.
 12. The method of claim 10,wherein a number of the taggant photoluminescent materials ranges from 1to 10, wherein the taggant photoluminescent materials comprisephosphorescent quantum dots, and wherein the phosphorescent quantum dotscomprise Cd/Se ligand stabilized fluorescent nano-crystals.
 13. Themethod of claim 10, wherein a number of the taggant polymeric additivesranges from 1 to 20, wherein the taggant polymeric additives comprisepolystyrene, and wherein an average molecular weight of the polystyreneranges from 500 to 20,000,000.
 14. The method of claim 10, wherein anumber of the taggant carbohydrates ranges from 1 to 10 and wherein thetaggant carbohydrates comprise glucose, fructose, sucrose, or lactose.15. The method of claim 10, wherein the chemical markers comprise thetaggant metal oxides or the taggant inorganic salts, wherein a number ofthe taggant metal oxides ranges from 1 to 20, or wherein a number of thetaggant inorganic salts ranges from 1 to 20, wherein the taggant metaloxides comprise titanium dioxide, zirconium oxides, zinc oxides,aluminum oxides, manganese oxides, magnesium oxides, calcium oxides, tinoxides, vanadium oxides, nickel oxides or iron oxide or wherein thetaggant inorganic salts comprise salts of cesium, indium, or samarium.16. The method of claim 1 and wherein each of the chemical markeramounts range from 100 ppb to 10,000 ppm, based on the weight of thefibers.
 17. The method of claim 1, wherein the fibers comprise acrylic,modacrylic, aramid, nylon, polyester, polypropylene, rayon,polyacrylonitrile, polyethylene, PTFE, or cellulose acetate.
 18. Themethod of claim 1, wherein the identification fibers comprise acrylic,modacrylic, aramid, nylon, polyester, polypropylene, rayon,polyacrylonitrile, polyethylene, PTFE, or cellulose acetate, and thestandard fibers comprise cellulose acetate.
 19. The method of claim 1,wherein the solvent comprises acetone, tetrahydrofuran, dichloromethane,methanol, chloroform, dioxane, N,N-dimethylformamide, dimethylsulfoxide, methyl acetate, ethyl acetate, nitric acid or pyridine. 20.The method of claim 1, wherein the analyzing comprises a use of massspectrometry, spectroscopy, nuclear magnetic resonance, or x-raydiffraction.
 21. The method of claim 1, wherein the analyzing comprisesa use of chromatography.
 22. The method of claim 1, wherein theanalyzing comprises a use of gas chromatography coupled to flameionization detection, size exclusion chromatography followed by UV-visspectroscopy, fluorescence spectroscopy, inductively coupled plasma(ICP) followed by mass spectrometry, or ICP followed by optical emissionspectrometry.
 23. The method of claim 1, further comprising (a)correlating one or more of the chemical markers and the taggant chemicalmarker amounts to a database, wherein the database comprisesmanufacturer specific taggants; and (b) determining the at least onesupply chain component of the fiber sample, wherein the at least onesupply chain component comprises a manufacturer of the fibers, amanufacture site of the fibers, a manufacturing line of the fibers, aproduction run of the fibers, a production date of the fibers, a packageof the fibers, a warehouse of the fibers, a customer of the fibers, aship-to location of the fibers, a manufacturer of a fiber bandcomprising the fibers, a manufacturing site of the fiber band, amanufacturing line of the fiber band, a production run of the fiberband, a production date of the fiber band, a package of the fiber band,a warehouse of the fiber band, a customer of the fiber band, or aship-to location of the fiber band.